Lab Manual 2013-R1

UEMK3431 Chemical Engineering Laboratory II
1
Faculty of Engineering and Science (FES)
Department of Chemical Engineering

UEMK3431
CHEMCAL ENGNEERNG
LABORATORY
MANUAL

Experiments:
1. Batch Reactor ........................................................................ 16
2. Continuous Stirred Tank Reactor {CSTR) ............................. 21
3. Plug Flow Reactor {PFR) ....................................................... 27
4. Level Process Control ............................................................ 33
5. Temperature Process Control ............................................... +0
6. Pressure Process Control ...................................................... +8
7. Flow Process Control ............................................................. 55
S. Disc Bowl Centrifuge ............................................................. 61
9. Fluid Mixing ............................................................................. 67
10. Fluidised Bed ........................................................................... 75
11. Bioprocess I........................................................................... 82
12. Bioprocess II......................................................................... 87

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13. X-Ray Diffractometer ........................................................... 9+
14. Sorptomatic ............................ 111
15. TPR Analysis........................................................................ 118


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Table of Content

1.0 UNIT OBJECTIVES ............................................................................................................. 4
2.0 UNIT OUTCOMES ............................................................................................................... 4
3.0 SUBJECT SYNOPSIS ........................................................................................................... 4
4.0 LABORATORY SAFETY, RULES AND REGULATIONS ............................................ 5
4.1 General Rules ............................................................................................................... 5
4.2 Laboratory Safety Rules .............................................................................................. 6
5.0 RESPONSIBILITY OF STUDENTS ................................................................................... 7
6.0 ASSESSMENTS ..................................................................................................................... 8
6.1 Breakdown of Marks ................................................................................................... 8
6.2 Overall Performance in Laboratory during Experiment Session (10 marks) .............. 8
6.3 Laboratory Reports (10 marks) .................................................................................... 9
7.0 LABORATORY REPORT WRITING ............................................................................. 10
7.1 Content ....................................................................................................................... 10
7.2 Specification .............................................................................................................. 12
7.3 Formatting .................................................................................................................. 13

Appendix A: Material Safety Data Sheet (MSDS)..123


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1.0 UNIT OBJECTIVES
This subject will help the students to develop their skills of collecting, analysing and presenting the
results of data acquired within a well-defined experimental system. The specific objectives are to:
combine elements of theory and practice particularly in chemical reaction, process control
fluid mechanics, bioprocess and catalysis,
familiarise with laboratory safety procedures,
develop and demonstrate a knowledge of experimental error analysis, probability and
statistics,
work collaboratively within a group setting,
develop skills in handling, manipulating and maintaining basic engineering machinery,
develop practical skills to plan and design laboratory experiments.

2.0 UNIT OUTCOMES
On completion of this unit, a student should be able to:
collect and analyse experimental data and its relationship to theoretical principles of
chemical reaction
control process
fluid mechanics
catalysis and bioprocess
operate laboratory experiments safely,
prepare a written laboratory report that clearly present the experimental results, analysis, and
relationship to theory,
develop skills in operating common chemical engineering equipment and measurement
apparatus.

3.0 SUBJECT SYNOPSIS
A laboratory course in pilot-scale processes involving chemical reaction, process control, fluid
mechanics, bioprocess and catalysis. Students will acquire the skills in project definition,
experimental operation, analytical procedures, data analysis and technical reports preparation.


5
4.0 LABORATORY SAFETY, RULES AND REGULATIONS
Laboratory safety is the top priority and this requires all people in the laboratory to be
observing safe practices at all times!

4.1 General Rules
Students must abide the dress code while working in the laboratory.
Laboratory coat must be worn all the time when working in the laboratory.
Only closed toe shoes are allowed in the laboratory. Do not wear sandals, slippers and high
heel shoes inside the laboratory.
Students with long hair must get their hair tied up tidily when doing laboratory work.
Bags and other belongings must be kept at the designated places.
Foods, drinks and smoking are strictly prohibited inside the laboratory.
Noise must be kept to the minimum as a courtesy to respect others.
Students are not allowed to work alone without the supervision of laboratory instructor/officer.
There must be at least 2 persons present in the laboratory at the same time.
Students are not allowed to bring any outsiders (non-registered parties) into the laboratory.
Any unauthorized experiment without the knowledge of laboratory instructor is prohibited.
All instrument and equipment must be handled with care.
Workspace has to be cleaned and tidied up after the experiment completed. Instrument and
equipment must be returned after used.
Students are strictly prohibited to take any equipment or any technical manuals out from the
laboratory without the permission of laboratory instructor/officer.
Students are required to instil an instinctive awareness towards property value of laboratory
equipment and to be responsible when using it. Any damages can cause to jeopardise the
success of not only the individual work but also to the university.
Do not attempt to remove and dismantle any parts of the equipment from its original design
without permission.
Students shall be liable for damages of equipment caused by individual negligence. If damages
occurred, an investigation will take place to identify the causes and the names of the involved
students will be recorded for faculty attention.
Please check the notice board regularly and pay attention to laboratory announcements.
Disciplinary action shall be taken against those students who are failed to abide the rules and
regulations.

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4.2 Laboratory Safety Rules
It is always a good practice and the responsibility of an individual to keep a tidy working
condition in laboratory.
It is important for each student to follow the procedures given by the laboratory instructor when
conducting laboratory experiment.
Before any experiment starts, students must study the information / precaution steps and
understand the procedures mentioned in the given laboratory sheet.
Students should report immediately to laboratory instructor/officer if the laboratory equipment
is suspected to be malfunctioning or faulty.
Student should report immediately to the laboratory instructor/officer if discovered any
damages on equipment or any hazardous situation.
Students should report immediately to the laboratory instructor/officer if any injury occurred.
If there is a tingling feel when working with electrical devices, stop and switch off the devices
immediately. Place a warning note before reporting to the laboratory instructor/officer and wait
for further instruction.
Do not work with electricity under wet condition in laboratory. Electric shock is a serious fatal
error due to human negligence and may cause death.
Students are required to wear goggles, gloves, apron and mask when handling corrosive or
active chemicals.
Hazardous chemicals must be properly stored and labelled in a designated place. Students must
acquire and study the material safety data sheet of a particular chemical before using it.
(Extracted from Student Laboratory Guidelines. Refer to UTAR Occupational Safety and Health website
www.utar.edu.my/osh for complete rules & regulations at the following link:
http://www.utar.edu.my/osh/file/Student%20Laboratory%20Guidelines1(07.09.08).doc)


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5.0 RESPONSIBILITY OF STUDENTS
Attendance is compulsory. Attendance shall be taken during the laboratory session.
Please sign your attendance when you attend the laboratory session.
Laboratory report can only be accepted for submission if the student has attended the
laboratory session.
Student must be punctual to attend laboratory session.
Students who are late for more than 30 minutes will be barred from attending the
laboratory session. Only students with valid reason of medical basis or unforeseen
circumstances can be considered to apply for laboratory replacement.
Students are expected to study the lab sheet before the laboratory session start.
Student must understand all the safety measures / precaution steps before starting any
experiments.
Student must complete the experiment within the allocated duration of laboratory session.
Students are responsible for the condition of their working area at the end of each laboratory
session. All power to the equipment and instruments should be turned off, and cooling water
flows should be shut off. Glassware used should be cleaned and dried.
Students have to pass up their experiment result to laboratory officer on the same day after
every experiment. A copy of the experimental result (with chop) must be attached together
with the laboratory report.
Fabricating results and plagiarism are strictly prohibited. Strict action will be taken if
student is found fabricating results or copy from others.
Students have to pass up their laboratory report (group report) 1 week after the date of
experiment to laboratory officer.

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6.0 ASSESSMENTS
6.1 Breakdown of Marks
Description Marks
Overall Performance during Experiment Session and Laboratory Reports 70%
Laboratory Test 30%

6.2 Overall Performance in Laboratory during Experiment Session (10 marks)
This is a group assessment. Each student performance in the laboratory during the experiment
session will be observed and marks will be given to the group as a whole.
The performance will be assessed based on the following criteria:
Criteria Description Marks
Safety
Awareness
Adhere to laboratory safety, rules and regulation.
Abide to dress code (lab coat, shoes, long pants etc.)
while working in the laboratory.
Understand all the safety measures / precaution steps
before starting any experiments.
Proper safety equipment such as goggles, gloves etc.
were used when necessary.
Show precautions when handling chemicals.
10
Punctuality Attend laboratory session on time.
Preparation Show understanding in the experiment that are about
to carry out.
Cleanliness and
Responsibility
Workspace is clean and tidied up after the
experiment completed.
Instrument and equipment are returned orderly after
use.
Show instinctive awareness towards property value
of laboratory equipment and instruments and their
responsibility in handling them.


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6.3 Laboratory Reports (10 marks)
Laboratory report will be assessed based on the following criteria:
Criteria Description Marks
Overall
Presentation
of Report
Organisation of report with the correct format and
necessary information such as titles, figure
explanations.
Report is written in clear and concise English.
2.5
Observations /
Data / Result
Presentation
Valid observations, consistent with event and
demonstrate attention to detail.
Data are presented in an organised manner.
Quality of data reflects students ability to perform
experiment successfully and utilise computer
software in analysis (if applicable).
All calculations and graphs are correct.
2.5
Discussion Discussion shows complete understanding of
experiment and the significance of data.
Logical explanation for problems in the data.
3.5
Conclusion Summary of key findings in a clear statement.
Clearly show relationships between data and
conclusion.
Express views on the weakness of the experimental
design (if there is any), or what is the implication of
the conclusion.
1.5
TOTAL 10


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7.0 LABORATORY REPORT WRITING
Laboratory reports are the most frequent document written by an engineering student. A laboratory
report should not be used to merely record the expected and observed results but demonstrate the
writers comprehension of the concept behind the data. A good laboratory report should address
the following questions:
Why? Why did I do this particular experiment?
How? How did I actually carry it out?
What? What did I find? What were my results?
So What? What does my result mean? What is the significance of the result? What are
my conclusions?

The goal of a laboratory report:
document your findings and
communicate their significance"

The laboratory report should be written with the same professionalism that would be used to
present the results of a major industrial project. A good report of technical work quantitatively
states significant results of experiments and computations and explains how they were obtained,
what they mean, and how they are useful. The report should be clear, concise, and accurate.

7.1 Content
The laboratory report should follow the following format and all the pages should be numbered
except the cover page.
Section
Max number of
lines / pages
UTAR Laboratory Cover Page
1) Title of Experiment 1 2 lines
2) Objectives of Experiment 1 5 lines
3) Introduction
Provide a scientific background related to the experiment and
provides the reader with justification for why the work was
carried out.
page


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Section
Max number of
lines / pages
4) Materials and Equipment
List only the materials/chemicals and equipment/apparatus used in
the experiment.
page
5) Results and Calculations
Present the data obtained from the experiment. The data have to
be presented in a clear and understandable manner.
All tables must be clearly labelled with numbers and titles.
All necessary calculations based on the raw data should be
provided in this section.
depends on
results and
calculations
6) Discussion
This is the most important section where detailed analysis of the
experimental data should be provided. Factors/issues related to
the obtained results must be explained.
Graphic materials based on the experimental data should be
presented and discussed in this section. All graphs must be
clearly labelled with numbers and titles.
Strategies that can use in the discussion:
compare expected results with those obtained
explain the results in terms of theoretical issues
what do the results indicate?
what is the significance of the results?
relate results to the experimental objectives
analyse experimental error
what ambiguities exist?
find logical explanation for problems in the data
what questions might we raise?
3 pages
7) Conclusion
Based on the discussion provided, summarise the key findings in a
clear statement. Additionally, the conclusion can also be used to
express views on the weakness of the experimental design (if
there is any), or what is the implication of your conclusion.
5 lines
8) References
List all references used in the preparation of the report.
Information obtained from any source, including the Internet, is
covered by copyright law. Any source referred in the report must
be acknowledged, both within the text and at the end of it.
The format should follow the American Psychological
Association (APA) referencing style.
depends on
references

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There shall be no appendix for the report. All information should be summarised into the
discussion section.

The laboratory reports should be arranged so as to include the major sections described above, but
students are free to insert additional subsections if they help to organise and clarify material and
information for the reader.

While the results and information contained in the report are of primary importance, students
should not underestimate the importance of a neat, easy-to-follow, well-organised presentation.
Pay attention to the appearance of the graphs, figures and tables, and to the ease with which the
reader can interpret them. Good results can be easily obscured by careless organisation and
presentation.

Students should take note on verb tense. These two points should help in writing the report:
By the time you get to the stage of writing a laboratory report, the experiment is already
finished. Use past tense when talking about the experiment.
Example: The objectives of the experiment were

The report, the theory and permanent equipment still exist; therefore, use present tense:
The objective of this report is..
Newtons Law of motion is.
The transmission electron microscope produces micrographs

7.2 Specification
Specification Description
Language The report should be written in British (UK) English.
Paper White simile A4 size paper (210 297 mm)
Printing Report must be computer typewritten using word processor and
printed preferably double sided.
Printing must be of high quality. Text and figures must be clear
and legible.
Binding Staple on top left corner


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7.3 Formatting
Formatting Description
Page Margin Left margin : 4.0 cm
Right, Top, Bottom margins : 2.5 cm
Header and Footer margins : 1.5 cm

Typesetting and
Spacing
Font Type : Times New Roman
Font Size : 12 pt
Section Title : Uppercase, Bold, Align left
Subsection Title : Title Case, Bold, Align left
Symbol for variable : Italic (e.g. m, P, T, v, , , )
General Spacing : 1.5 lines
General alignment for texts in paragraph should be justified.

The format for writing units, symbols, numbers etc. in the report follows the International System
of Units (SI). The following sections give some common descriptions of the writing styles. For
complete and thorough information, refer to the SI Brochure available online at
http://www.bipm.org/en/si/si_brochure/.
The use of the correct symbols and names for SI units, and for units in general are mandatory in the
report. In this way ambiguities and misunderstandings in the values of quantities can be avoided.
Style Description
Numbers Avoid starting a sentence with a number or symbol.
Number has to be used together with unit; if not it has to be spelled out
(e.g. three cats; not 3 cats).
If the number is between +1 and -1, the decimal marker is always
preceded by a zero (e.g. 0.15; not .15).
Numbers with many digits may be divided into groups of three by a
thin space, in order to facilitate reading. Neither dots nor commas are
inserted in the spaces between the groups (e.g. 43 765 589, 58.159 25;
not 43,765,589; not 58.159,25).
When there are only four digits before or after the decimal marker, it is
customary not to use a space to isolate a single digit (e.g. 5879, 1.5681)
When multiplying numbers, use only the multiplication sign with a
space before and after, not centre dot ( ) nor the letter x or X (e.g.
25 5.3; not 25 5.3; not 25 x 5.3).


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Style Description
Units If possible, use SI units; although other commonly used non-SI units are
also acceptable (e.g. C for temperature, bar for pressure).

Spacing
One spacing between number and unit (e.g. 5 cm, 50 C, 30 %; not
5cm; not 50C; not 30%).
Exception for angular degree (), minute () and second () (e.g. 3, 45)
which are placed immediately after the number.

Symbols for Units
Use symbol for units and not their abbreviation (e.g. 5 s; not 5 sec.).
Symbols for units are written in upright type i.e. not italic (e.g. m for
metres, g for grams). This is to differentiate them from italic type
symbols used for variables (e.g. m for mass).
Symbols for units are written in lowercase, except for symbols derived
from the name of a person, which start with uppercase. However, the
unit name itself is written in lowercase.
(e.g. the unit for pressure is named after Blaise Pascal; the unit itself is
written as pascal whereas the symbol is Pa; 5 Pa or 5 pascal; 5 J or
5 joule; 5 N or 5 newton)
Symbols are not pluralised (e.g. 5 kg; not 5 kgs).
Symbols do not have an appended period / full stop (.) unless at the end
of a sentence.
Symbols derived from multiple units by multiplication are joined with a
space or centre dot ( ) (e.g. N m for Nm). Hyphens (-) should not be
used (e.g. not N-m)
[Note: centre dot ( ) is different from period / full stop (.); centre dot is
available under command Insert > Symbol].
Symbols formed by division of two units are joined with a solidus ( )
(slash ( / ) is also acceptable) or given as a negative exponent (e.g. m/s
or m s
-1
).
Only one solidus should be used (e.g. kgm
-1
s
-2
or kg/(ms
2
); not
kg/m/s
2
).
Do not mix unit symbols and unit names within one expression (e.g.
coulomb per kilogram; not coulomb per kg).


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Style Description
SI Prefixes

Factor Name Symbol Factor Name Symbol
10
1
deca da 10
1
deci d
10
2
hecto h 10
2
centi c
10
3
kilo k 10
3
milli m
10
6
mega M 10
6
micro
10
9
giga G 10
9
nano n
10
12
tera T 10
12
pico p
10
15
peta P 10
15
femto f
10
18
exa E 10
18
atto a
10
21
zetta Z 10
21
zepto z
10
24
yotta Y 10
24
yocto y

Prefix symbols are attached to unit symbols without a space or hyphen
(-) between the prefix symbol and the unit symbol (e.g. km; not k m;
not k-m).
The same also apply for prefix names (e.g. kilometre; not kilo metre;
not kilo-metre)
Prefix symbols are written in upright type, i.e. not italic. (e.g. kPa; not
kPa).
All prefix symbols larger than kilo (10
3
) are uppercase; the rest are
lowercase (see table above) (e.g. MW, GHz, kW, mg, nm).
All prefix names are lowercase, except at the beginning of a sentence
(e.g. megawatt, gigahertz, kilowatt, milligram, nanometre)
A prefix is never used in isolation; and compound prefixes are never
used (e.g. 10
-9
m is nm or nanometre; not mm or millimicrometre).

UEMK3431 Chemical Engineering Laboratory II Exp 1: Batch Reactor

16
Experiment 1
Batch Reactor

1.0 OBJECTIVES OF EXPERIMENT
To determine the reaction rate of saponification reaction at given temperature by measuring
the conversion against reaction time.
To evaluate the reaction rate constant at constant temperature using differential and integral
methods of analysis.
To evaluate the rate constant at different temperatures and activation energy determination
from Arrehenius Plot.

2.0 INTRODUCTION
In batch reactions, there are no feed or exit streams and therefore the mass balance equation for
species A in an element of reactor volume V obeys the following statement:

Rate of A produced within volume element = Rate of A accumulated within volume element

In a batch reactor, the process in the reactor is at unsteady state by its nature. In this process, one or
more variables vary with time. The longer the reactant is in the reactor, the more reactant is
converted to product until either equilibrium is reached or the reactant is exhausted.

2.1 Theory
In a constant volume reactor, volume element means the volume of reaction mixture, and not the
volume of reactor. Thus, this term means a constant-density reaction system. Most liquid phase
reactions as well as gas phase reactions occurring in a constant volume reactor falls in this class.

In Constant Volume System:

dt
dC
V
dt dN
r
i i
i
= =
/
(1)

Thus, the rate of reaction of any component is given by the rate of change of its concentration or
partial pressure no matter how we choose to follow the progress of the reaction.

Suppose that N
Ao
is the initial amount of A in the reactor at time t = 0, and that N
A
is the amount
present at time t. The conversion of A in the constant volume system is then given by

( ) ( )
Ao
A Ao
Ao
A Ao
A
C
C C
N
N N
X

=
= (2)


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The rate of reaction (disappearance of component A), is, in general given by

V
dt dN
r
A
A
/
= (3)

dt
dX
N V r
A
Ao A
= (4)

Integrating the above equation gives,

( )
}

=
V r
dX
N t
A
A
Ao
(5)

where t is the time required to achieve a conversion X
A
for either isothermal or non-isothermal
operation.

dt
dX
C r
A
Ao A
= (6)

The time t necessary to achieve a conversion X
A
is:

}

=
A
A
Ao
r
dX
C t
(7)

In terms of concentrations, if the density of the fluid remains constant.

}

=
A
A
r
dC
t (8)

Figure 2.1 shows the graphical representation of batch reactor Equation (8),

Figure 2.1: Reaction Rate Constant is almost always strongly dependent on Temperature

) (
1
A
r
C
A

C
A0
C
A

Area = t

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The Arrhenius Law is given by

k (T) = Ae
E / RT
(9)

where A = pre-exponential factor of frequency factor
E = activation energy, kJ/mol or cal/mol

3.0 EQUIPMENT BATCH REACTOR

Figure 3.1: Batch Reactor

4.0 OPERATING PROCEDURES
4.1 Pre-experiment Procedures
1. Read and understand the theory of batch reactor.
2. Read and understand the equipment used in the experiment (batch reactor).
3. Read the safety precautions and chemical hazards before conducting the experiment.
4. Read the Material Safety Data Sheet (MSDS) for the chemicals used in the experiment in
Appendix A.
5. Prepare the following apparatus and materials needed for the experiment:
Beaker: 2 L 1, 1 L 1, 250 mL 2
Measuring Cylinder: 100 mL 2
Glass rod
Conductivity Meter
Electric Stirrer
Overhead Stirrer
Water Bath
Beaker (2L)
Conductivity Meter
Beaker (1L)

19
Water bath
Stopwatch
5 L of 0.1 M sodium hydroxide, NaOH
2 L of 0.1 M ethyl acetate, Et(Ac)
500 mL of 0.1 M sodium acetate, Na(Ac)
1 L of deionised water, H
2
O

5.0 CHEMICAL HAZARDS, SAFETY AND PRECAUTIONS
5.1 Chemical Hazards (refer MSDS in Appendix A for more details)
Sodium hydroxide (NaOH) solid and its solutions are corrosive. Spilled chemicals may damage
the apparatus. Contact with skin can cause burn and contact with the eyes can cause serious
long-term damage. Significant heat is released when NaOH dissolves in water.
Ethyl acetate (Et(Ac)) is very flammable, so constitutes a fire risk. It can be ignited by flames,
but also by contact with items such as hot plates or hot air guns.
Ethanol (EtOH) is very flammable, so constitutes a fire risk. Ethanol contact with the eyes can
cause considerable irritation.
Sodium acetate (Na(Ac)) may be harmful if a large amount is swallowed.

5.2 Safety Precautions
Always wear safety glasses, mask and gloves when handling chemicals. Do not allow the
solution to come into contact with your skin or eyes.
Should any chemicals come into contact with the body, rinse off immediately with plenty of
water and inform the laboratory instructor/officer. Seek medical treatment if symptoms persist.
Wash away any splashes of chemical immediately.
Do not touch the reactor when in operation and beware of scalding.
Ensure proper ventilation in laboratory. No open flames or hot items in the vicinity.
Dispose of all unused chemicals in an appropriate manner after the experiment. Under no
circumstances should the chemicals be allowed to flow into sinks or drains.
Wash your hands thoroughly with soap after the experiment.


20
6.0 EXPERIMENTS
6.1 Experiment 1: Calibration Curve Conductivity versus Conversion
The reaction to be studied is the saponification reaction of ethyl acetate Et(Ac) and sodium
hydroxide NaOH. Since this is a second order reaction, the rate of reaction depends on both the
concentrations of Et(Ac) and NaOH. However, for analysis purposes, the reaction will be carried
out using equimolar feeds of Et(Ac) and NaOH solutions with the same initial concentrations. This
ensures that both concentrations are similar throughout the reaction.

NaOH + Et(Ac) Na(Ac) + EtOH

Create a calibration curve: conductivity vs conversion for the reaction between 0.1M Et(Ac) and
0.1M NaOH.

6.2 Experiment 2: Determine the Rate of Reactions
Setup the apparatus as per Figure 3.1. Conduct the experiment with at least Four different
temperatures.

7.0 RESULTS ANALYSIS AND DISCUSSION
Discuss all your results. The questions below only serve as a guideline. Your discussion should
not only limit to these questions.
1. Evaluate the rate constants for forward and reverse reaction treating the saponification reaction
as reversible reaction.
2. What is the time required for 95% conversion?
3. What are the advantages and disadvantages of obtaining kinetic data in a batch reactor?
4. What is the most appropriate method of continuously monitoring the concentration of reactants
during saponification reaction?

UEMK3431 Chemical Engineering Laboratory II Exp 2: CSTR

21
Experiment 2
Continuous Stirred Tank Reactor (CSTR)

To observe and control the operation of a continuous-stirred tank reactor.
To determine the effects of flow rate on conversion rate in a continuous-stirred tank reactor.

2.0 INTRODUCTION
The main feature of CSTR is that mixing is complete so that properties such as temperature and
concentration of the reaction mixture are uniform in all parts of the reactor. By studying the rate
data for saponification reaction of ethyl acetate and sodium hydroxide to form sodium acetate in a
continuous stirred tank reactor (CSTR), one can design a CSTR from the rate data.

In kinetic studies each steady-state run gives, without integration, the reaction rate for the
conditions within the reactor. The ease of interpretation of data from a CSTR makes its use very
attractive in kinetic studies.

The reaction rate constant can be evaluated from the reaction rate data at a given temperature. The
rate data analysis depends on the type of reaction and rate constant can be evaluated by integral
method of analysis. The rate constant is determined at different temperatures. The effect of mixing
over kinetic data in CSTR is also determined. The reaction activation energy can be determined
from Arrhenius plot of reaction rate constant against reaction temperature.

2.1 Theory
The reaction rate constant is independent of the concentrations of the species involved in the
reaction and strongly dependent on the temperature. The reaction rate constant dependence on
temperature is given as

|
.
|
\
|
=
RT
E
A T k exp ) ( (1)

where A = pre-exponential factor of frequency factor
E = activation energy, kJ/mol or cal/mol

The conservation principle requires that the mass of species A in an element of reactor volume V
obey the following statement:


22
(
=
(
+
(
element ume within vol

d accumulate A of Rate
element ume within vol
produced A of Rate
element volume
of out A of Rate
element volume
into A of Rate

Applying the above equation to CSTR with no accumulation of material A in the reactor, the CSTR
volume necessary to achieve a specified conversion X
A
is

( )
A
A A
r
X F
V
=
0
(2)

where F
A0
= initial feed rate of A
r
A
= rate of reaction

Since the exit composition from the reactor is identical to the composition inside the reactor, the
rate of reaction is evaluated at the exit conditions.

For a typical reaction

Products B A +
k
(3)

the rate of reaction (r
A
) treating the reaction as first order with respect to A and B is

( )( )
A A A
B A A
X X kC
C kC r
=
=
1
02
(4)

Assuming C
B0
= C
A0
, M
0
= C
B0
/C
A0
= 1, C
B0
C
A0
= C
A0
2
.

Once the rate of reaction (r
A
) is obtained from Eq. (2), the value of k can be obtained from Eq. (4).

Consider a chemical reaction between ethyl acetate and sodium hydroxide. This process is also
known as saponification. The reaction is reversible, and is described by

CH
3
COOCH
2
CH
3
+ NaOH HOCH
2
CH
3
+ CH
3
COONa
(ehtyl acetate) (sodium hydroxide) (ethanol) (sodium acetate)

The ethyl acetate molecules split into acetate ions and ethanol molecules, consuming hydroxide
ions provided by sodium hydroxide in the process. The progress of the reaction can thus be tracked
accurately by the change in hydroxide ions. This can be observed by the conductivity change in the
reactor vessel, since the presence of hydroxide ions increase the conductivity in a solution.

As the conversion increases, the hydroxide ions deplete to form ethanol, and this should be
observed by a decrease in conductivity. The percentage conversion of the reactants can thus be
determined from the conductivity values as follows:


23

( )
( )
% 100 1
(
=
e o
e
X

(5)

where = measured value for conductivity (mS/cm)

o
= initial conductivity for 2.3% sodium hydroxide solution (128.2 mS/cm)

e
= conductivity of the end product (1 mS/cm for a 5% sodium acetate solution)

It can be observed that for each mole of sodium acetate and ethanol produced, one mole of ethyl
acetate and sodium hydroxide is consumed.

3.0 EQUIPMENT CONTINUOUS STIRRED TANK REACTOR (CSTR)
This CSTR unit is used to demonstrate the basics of chemical processing in continuous flow
reactors. The apparatus comprised of two glass feed tanks, a chemical reactor, a cooling/heating
water reservoir, pumps and a process control console.

The reactant tanks are provided with heating coils to bring reactants to reaction temperatures before
dosing into the reactor. The dosing peristaltic pumps are fitted with speed controls to adjust the
feeding rate while the control console is fitted with a temperature control, conductivity meter and a
stirrer control unit.

A - Main Power Switch
B - Conductivity and
Temperature Meters
C - Hot Water Pump
D - Sump Tank
E - Hot Water Tank
F - NaOH Feed Tank
G - Et(Ac) Feed Tank
H - Reactor Vessel
I - Dosing Pumps
J - Tank Drain Valves
K - Hot Water Valves
L - Pump Bypass Valve
Figure 3.1: Continuous Stirred Tank Reactor

J
K
L

24
1. Read and understand the theory of CSTR.
2. Read and understand the equipment used in the experiment (CSTR).
Appendix A.
Beaker: 2 L 2
Measuring Cylinder: 100 ml 1
Volumetric Flask: 1 L 1
Glass rod
Stopwatch
15 L of 2.3% sodium hydroxide (NaOH) solution
15 L of 5% ethyl acetate (Et(Ac)) solution
2
O



25
Ensure that the drain valves (J) for the sump tank and hot water tank are fully closed.
Ensure that the drain valve for the reactor vessel (H) is fully closed.
Ensure that all the hot water valves (K) are fully closed. Leave the pump bypass valve (L)
partially open.
Fill the hot water tank with water until 80% full.

6.0 EXPERIMENTS


0.1M NaOH.

6.2 Experiment 2: Determine the Effects of Flow Rate on Conversion Rate
Prepare the equipment until the set temperature. Conduct the experiment with at least Three
different dosing rates.


26
1. Define residence time. How do you determine the residence time of a CSTR with fixed
volume?
2. How does the volume of a CSTR affect the conversion of reactants into products?
3. Does temperature affect the conversion and conversion rate? Discuss the temperature effects
on chemical reactions.
4. Le Chateliers principle states that chemical reactions favour the direction which opposes
changes to a system in equilibrium. How would you increase the conversion in a system that
produces ammonia? (Note - the production of ammonia from nitrogen and hydrogen gas is
exothermic.)

UEMK3431 Chemical Engineering Laboratory II Exp 3: PFR

27
Experiment 3
Plug Flow Reactor (PFR)

To carry out a saponification reaction between NaOH and Et(Ac) in a PFR.
To determine the reaction rate constant.
To determine the effect of residence time on the conversion in a PFR.

2.0 INTRODUCTION
The plug flow reactor (PFR) (or sometimes called the tubular flow reactor (TFR)) is commonly
used in industry in addition to continuous stirred tank reactor (CSTR) and batch reactor. It consists
of a cylindrical pipe and is normally operated at steady state. For analysis purposes, the flow in the
system is considered to be highly turbulent and may be modelled by that of plug flow. Thus, there
is no radial variation in concentration along the pipe.

In a PFR, the reactants are continually consumed as they flow down the length of the reactor. In
modelling a tubular reactor, the concentration is assumed to vary continuously in the axial direction
through the reactor. Consequently, the reaction rate, which is a function of concentration for all but
zero order reactions, will also vary axially.

2.1 Theory

Figure 2.1: Plug Flow Reactor

To develop the PFR design equation, the reactor volume shall be divided into a number of sub-
volumes so that within each sub-volume V, the reaction may be considered spatially uniform.
Assuming that the sub-volume is located a distance y from the entrance of the reactor, then F
A
(y) is
the molar flow rate of A into volume V and F
A
(y + y) is the molar flow rate of A out of the
volume.

F
A0
F
A

F
A
(y)
V
F
A
(y+ y)
y
y

28
In a spatially uniform sub-volume V,

}
=
V
A A
V r dV r (1)

For a plug flow reactor at steady state, the general mole balance is reduced to

0 =
dt
dN
A

0 ) ( ) ( = + + V r y y F y F
A A A
(2)

In the above expression, r
A
is an indirect function of y. That is, r
A
is a function of reactant
concentration, which is a function of the position, y down the reactor. The volume, V is the
product of the cross-sectional area, A of the reactor and the reactor length, y,

y A V = (3)

Substituting Eq. (3) into Eq. (2) and taking the limit as y approaches zero yields

A
A A A
y
Ar
dy
dF
y
y F y y F
= =
(
+

) ( ) (
lim
0
(4)

It is usually most convenient to have the reactor volume, V rather than the reactor length, y as the
independent variable. Accordingly, the variables Ady can be changed to dV to obtain this form of
the design equation for a PFR,

A
A
r
dV
dF
= (5)

Note that for a reactor in which the cross-sectional area, A varies along the length of the reactor, the
design equation remains unchanged. This means that the extent of reaction in a plug flow reactor
does not depend on its shape, but only on its total volume.

If F
A0
is the molar flow rate of species A fed to a system operating at steady state, the molar flow
rate at which species A reacting within the entire system will be F
A0
X. The molar feed rate of A to
the system minus the rate of reaction of A within the system equals the molar flow rate of A leaving
the system, F
A
. This is shown in mathematical form to be

( ) X F X F F F
A A A A
= = 1
0 0 0
(6)


29
The entering molar flow rate F
A0
is just the product of the entering concentration C
A0
and the
entering volumetric flow rate V
0
,

0 0 0
V C F
A A
= (7)

A A
r
dV
dX
F =
0
(8)

Rearranging and integrating Eq. (8) with the limit V = 0 when X = 0, we obtain the plug flow
reactor volume necessary to achieve a specified conversion X,

}
=
X
A
A
r
dX
F V
0
0
(9)

3.0 EQUIPMENT PLUG FLOW REACTOR
This Plug Flow Reactor has been designed for experiments on chemical reactions in liquid phase
under isothermal and adiabatic conditions. The unit comes complete with a jacketed plug flow
reactor, individual reactant feed tanks and pumps, temperature and conductivity measuring sensors.

V1
V5
FI
02
TIC
01
V7
V14
Pump
P1
Feed
Tank
B1
(30-L)
Feed
Tank
B2
(30-L)
Pump
P2
LS1
LS2
Vent
Tubular
Reactor
R1
(0.4-L)
M1
V13
V19
V20
Drain
Waste Tank
B3
(60-L)
Water
De-ionizer
c.w.
Pump
P3
V17
V18
V11
V10 V12
V15
QI
02
V9
FI
01
Drain
Drain
Drain
Sampling
QI
01
V8
V4
V3
V16
Water
Jacket
B4
(10-L)
Pre-heater
B5
(3-L)
Electrical
Cart. Heater
W1, W2
(2x1.0 kW)
V2
V6
c.w.
V21
Drain
TI
02

Figure 3.1: Process Flow Diagram for Plug Flow Reactor Unit


30
1. Read and understand the theory of plug flow reactor.
2. Read and understand the equipment used in the experiment (plug flow reactor).
Appendix A.
Beaker: 100 mL 2
Measuring Cylinder: 50 mL 2
Conical Flask: 250 mL 2
Burette
pH Indicators
30 L of 0.1 M sodium hydroxide, NaOH
30 L of 0.1 M ethyl acetate, Et(Ac)
1 L of 0.25 M Hydrochloric Acid, HCl
2
O

4.2 General Shutdown Procedures
1. Switch off all the pumps P1, P2 and P3. Close valves V2 and V6.
2. Switch off the stirrer.
3. Switch off the main power switch at the control panel and power supply.
4. Dispose all chemicals into the container provided.


31

E Ensure that the drain valve (V16) of waste tank B3 is fully closed.
Ensure that all valves are initially closed except pump bypass valves V3, V7 and V17.
Fill feed tank B1 with the NaOH solution and feed tank B2 with the Et(Ac) solution.
Fill up the water jacket B4 and pre-heater B5 with clean water.

6.0 EXPERIMENTS


0.1M NaOH.

32
Experiment 2: Investigate the Effect of Residence Time on the Reaction in a PFR
Conduct the experiment with Five different flow rates (ensure both feed flow rates are the same all
the time). Record both the inlet and outlet steady state conductivity values then collect a 50 ml
sample and immediately run Experiment 3.

Reminder:
Open valves V2 & V6 (feed pumps suction), V4 & V8 (feed pumps discharge), and V9 & V11
(feed to reactor). Switch on both the feed pumps P1 and P2. Adjust valves V4 and V8 to obtain the
pre-set flow rate. Then close valves V9 and V11 follow by open valves V13 & V18 (pump P3
suction and discharge), and switch on pump P3 (to circulate the water through pre-heater B5) and
stirrer. Lastly, open valves V9 and V11 again where allow both solutions to enter reactor R1 and
overflow into the waste tank B3. Record the flow rates of the feeds and start monitoring the inlet
(QI-01) and outlet (QI-02) conductivity.

6.2 Experiment 3: Back Titration
This experiment is carried out to verify the conductivity on the conversion of NaOH in the reactor.
It is based on the principle of quenching the sample (from Exp 2) with excess acid (10 ml 0.25M
HCl) to stop any further reactions and then back titrating with a base (0.1 M NaOH) to determine
the amount of unreacted acid.

Determine the different reactor residence times, the value of the reaction rate constant, k and the
rate of reaction, r
A
.

UEMK3431 Chemical Engineering Laboratory II Exp 4: Level Control

33
Experiment 4
Level Process Control

To understand the characteristic of proportional (P), proportional-integral (PI) and
proportional-integral-derivative (PID) controller in a level control loop.
To observed the different types of process level responses to P, PI and PID controller.
To determine the optimum controller tuning parameter(s) for P, PI and PID controller.

2.0 INTRODUCTION
A fundamental component of any industrial process control system is the feedback control loop. It
consists of the process, the measurement, the controller, and the final control element. If all these
elements are interconnected, that is, if information can be passed continuously around the loop, this
is closed-loop control and automatic feedback generally exists.

Automatic control requires signal system to close the loop and provide the means for information
flow. This means that the controller must be able to move the valve, the valve must be able to
affect the measurement, and the measurement signal must be reported to the controller. Without
this feedback, we do not have automatic control.

2.1 Proportional Control
When a process has small capacity, it usually responds quickly to upsets. Proportional control
attempts to stabilise the system and avoid fluctuations by responding to the magnitude as well as
the direction of the error.

The relationship between the output and the width of the measurement span is called the
proportional band (PB) and is expressed in percentage. For example, a 20% proportional band is
narrow; it provides sensitive control because 100% output change is produced by only 20%
measurement change. Conversely, a 500% proportional band is very wide with only 20% of the
possible output produced by 100% change in measurement.

The proportional controller calculates the amount of error between the measurement and set point,
amplifies it, and positions the final control element to reduce the error. The magnitude of the
corrective action is proportional to the error. When there is a process upset, the valve must change
position to keep the controlled variable at the set point. The output from the controller (which
controls the valve position) must assume a new value, different from the original (the set point),
before equilibrium can again be reached. This new value of the controlled variable is offset from
the set point.

Curve C in Figure 2.1 shows system response when the proportional band in which the oscillations
settle out quickly. If the PB is too wide (insensitive), the offset will be much larger, reducing the

34
amount of control over the process. Narrowing the PB (increasing the gain) can reduce the amount
of offset, but too narrow a band will creates cycling.

Figure 2.1: Proportional Only System Response to a Process Upset with Different
Proportional Band Widths

2.2 Proportional-Integral (PI) Control
Integral action avoids the offset created in proportional control by bringing the output back to the
set point. It is an automatic rebalancing of the system, which operates as long as an error exists.
Therefore, integral control responds to the duration of the error as well as its magnitude and
direction. Integral control is almost never used alone; rather, it is combined with proportional
control.

Proportional-plus-integral (PI) control is generally used on processes where no amount of offset can
be tolerated. Other applications include those where such a wide PB would be required for stability
that the amount of offset created would be unacceptable. When a process upset occurs, the
proportional controller registers an error and responds to it as shown in Figure 2.2. The integral
control mode detects the offset error in the proportional mode and tries to eliminate the error.

In PI controller, integral action can be expressed in terms of minutes per repeat the amount of
time necessary to repeat the response caused by the proportional mode for a step change in error.
The smaller the time value, the faster the integral action. Some controller manufactures express
integral action in repeats per minute, which is the reciprocal of minutes per repeat.

Ideally, the minutes per repeat chosen for the integral controller should bring the control point back
to the set point quickly. If the integral time is too long, the system will not perform at maximum
efficiency. If the time is too short, it will overshoot the set point and a continuous cycle may result.

One problem with integral control is that when a deviation cannot be eliminated over a period of
time (as with batch processes when a tank is empty), the controller continues to see an error and
tries to correct for it, saturating it and driving the output to its maximum value. This is called
integral windup.


35

Figure 2.2: PI Control System Response to a Process Upset with Different Integral Times

2.3 Proportional-Integral-Derivative (PID) Control
The proportional and PI controller have limitations which may not be significant if the process and
controller are carefully matched. However, some processes are so difficult to control or so critical
to maintain at set point, that the use of all three modes will be helpful in maintaining desired control.

PID control responds to all aspects of process error direction, magnitude, duration and rate of
change. The output of a PID controller is a linear combination of P, I, and D modes of control.
PID control can be advantageous on many processes. Processes that benefit most from PID control
have rapid and large disturbances in which derivative action can respond to the rapidity of the
changes, and integral action can respond to the its duration.

Derivative action permits an increase in proportional gain, offsetting the decrease necessitated by
integral action; where integral action tends to increase the period of cycling, derivative action tends
to reduce it, thereby producing the same speed of response as with proportional action but without
offset.

Figure 2.3 shows the effect of the addition of derivative action to a properly adjusted PI controller.
The period (time to complete a cycle) is shorter than with PI-only control.

Figure 2.4 shows the response of a system to a process upset in the primary analogue control mode:
proportional, integral, and PID.


36

Figure 2.3: Comparison of System Response to a Process Upset with PI and PID Control

Figure 2.4: System Response to a Process Upset with Different Modes of Analogue Control

3.0 EQUIPMENT LEVEL CONTROL UNIT/TRAINER
The Level Control Unit/Trainer consists of a process vessel connected to main reservoir with water
pump, level sensor and electro-pneumatic proportional control valve (air supplied by a compressor).
The liquid level rate is monitored by the sensor with digital signal output to the monitoring console
at the computer.

An electronic controller is connected to the computer software for data logging and remote control.
The proportional, PI and PID modes are preset into the system. The PID parameter may be
continuously varied for optimum controller tuning. Demonstration of disturbance effect on the tank
water level may be done with a disturbance valve to reduce the level in the tank.


37

A - Process Tank Level
Indicator
B - Process Tank
C - Pneumatic Pressure
Regulator
D - Level Sensor
E - Water Pump
F - Control Panel
G - Electro-pneumatic
Rotary Actuator with
Positioner (proportional
valve)
H - Reservoir Tank
I - Disturbance Valve

4.0 OPERATING PROCEDURE
1. Read and understand the theory of level process control.
2. Read and understand the equipment used in the experiment (level control unit).
3. Read the safety precautions before conducting the experiment.

4.2 General Start-Up Procedures
1. Fill the reservoir tank (H) with water to at least 3/4 of its maximum height.
2. Ensure that the disturbance valve (I) is in fully closed position.
3. Ensure that the pneumatic pressure regulator (C) is connected to the air compressor. Set the
pressure to 0.25 MPa ~ 0.3 MPa.
4. Ensure that the communication cable is connected from the side of the apparatuss control
panel (F) to computer PCI slot.


38
1. Switch off the water pump (E).
2. Switch off the power at the control panel and the main power supply.
3. Turn off the compressed air supply valve at the compressor and switch off the compressor
main power supply.

5.0 SAFETY PRECAUTIONS
Do not switch on the water pump if there is no water in the reservoir tank or the water level is
low.
Do not apply pressure more than 0.4 MPa to the electro-pneumatic proportional valve.
Do not attempt to change the setting of the control valve and sensor.
Switch off the apparatus if there is any water leakage.

6.0 EXPERIMENTS
Conduct the experiment with closed loop control without PID tuning and level value at 100 mm.

Reminder:
Click the Start button and save the file before turn on the water pump (E). WARNING: keep an eye
on the process tank level indicator (A) on the right hand side of the equipment. Stop the pump
immediately if the tank level reaches 250 mm to avoid tank overflow.
Press Alt + Print Screen button on the computer keyboard and paste the graph in Paint or WordPad.

6.1 Experiment 1: Proportional-only (P) Mode
Run the experiment with different P values (1 to 100).

39
6.2 Experiment 2: Proportional-Integral (PI) Mode
Run the experiment with different I values (0.05 to 2).

6.3 Experiment 3: Proportional, Integrative, Derivative (PID) Mode
Run the experiment with different D values (0.05 to 2). Adjust all the three parameters to achieve
the best system response.

7.0 RESULTS ANALYSIS AND DISCUSSIONS
Compare all the graphs obtained and explain the effect of the P, I and D action on the set-point
selected. Figure out the system overshoot percentage and settling time.

UEMK3431 Chemical Engineering Laboratory II Exp 5: Temperature Control

40
Experiment 5
Temperature Process Control

proportional-integral-derivative (PID) controller in a temperature control loop.
To observed the different types of temperature responses to P, PI and PID controller.

2.0 INTRODUCTION

2.1 On/Off Control
On/Off control is generally both the simplest and the least expensive type of process, but response
of an on/off controller almost always has some error in it. The controller turns on or off only when
the measurement crosses its set point on its way from one extreme error to another. At that point,
the valve goes either fully open (on) or closed (off), depending on the direction of the error. The
size of the error is not recognised and the energy or material supplied to the process is always either
too much or not enough. The measured variable also cycles continuously. On/Off control best
applied to a large capacity process that has relatively little dead time and a small mass or energy
inflow with respect to the capacity of the system.

Figure 2.1: System Response to a Process Upset with ON/OFF Control


41


the set point.




42
control.






offset.


43




2.5 Control Loop Tuning
Tuning process adjusts the controlled variable to the set point so it can achieve that balance as
quickly as possible. This is done when the instrument is first put in service and, later, on a periodic
basis, tune as part of preventive maintenance. When tuning, remember that each controller is part
of a closed loop: all the parts of the loop are interactive. The controller response must be matched

44
to that of the process. There are several procedures for doing this, some mathematical, most using
trial and error.

3.0 EQUIPMENT TEMPERATURE CONTROL UNIT/TRAINER
The Temperature Control Unit/Trainer consists of a heat exchanger with two input/output ports for
hot and cold water as the medium. Water is heated by a submersion heater in the hot water tank
and is circulated in the system by pump P1. Cold water, supplied by the cold water tank which
connects directly to a water supply, is pump into the heat exchanger by pump P2 and then discharge
into drain.

Temperature transmitter TT01 is used to measure the cold water outlet temperature from the heat
exchanger and is linked to a microprocessor based controller. The controller output is linked to a
pneumatic control valve (air supplied by a compressor) to manipulate the hot water flow rate into
the heat exchanger which will affect the cold water outlet temperature.

The unit is supplied with a chart recorder. The pump has its own starter. The control panel and
patch panel are safely protected against water splashes.

Figure 3.1: Schematic Diagram of Temperature Control Unit / Trainer


45
1. Read and understand the theory of temperature process control.
2. Read and understand the equipment used in the experiment (temperature control unit).

1. Switch ON the computer and start the temperature control unit software (SE-404).
2. Ensure that all valves are set according to the position outlined in table below:
Open Close Partially Open
HV1
(hot water pump inlet)
HV3
(cold water tank drain valve)
HV2
(hot water pump bypass)
HV6
(cold water pump inlet)
HV4
(hot water tank drain valve)
HV7
(cold water pump bypass)
HV9
(cold water discharge to drain)
HV5
(hot water tank supply valve)

HV10
(cold water tank supply valve)

3. Fill up Tank TN1 and TN2 with water by opening valve HV5 and HV10 until the tanks are full.
Close valve HV5 and leave valve HV10 open.
4. Turn on the power supply and main power switch at the front of the control panel
5. Turn on the water heater.
6. Set the temperature controller TIC 02 set point to 55C and wait until the temperature reaches
55C (temperature of hot water tank).
7. Switch on Pump P2 and adjust the flow rate to ~ 5 LPM by using valve HV8.
8. Turn on the hot water circulation pump P1.
9. The unit is now ready.

1. Switch off pump P1, P2 and water heater E1.
main power supply.
4. Turn off the main water supply.

46
Do not switch on the water pump if there is no water in the tank or the water level is low.
Do not apply pressure more than 0.4 MPa to the electro-pneumatic proportional valve.

6.0 EXPERIMENTS
6.1 Experiment 1: Closed Loop Proportional (P) Control
6.1.1 Load Change
Simulate a load change by increasing the cold water flow rate for 20 seconds by using valve HV8.
Repeat the experiment with Three different PB values while keeping the I and D values constant.

Reminder:
Start with Manual Mode where Proportional (PB) value of 100, Integral (I) value of 600 seconds
and Derivative (D) value of 0 second. Set the Set Point value and slowly adjust the control valve
opening until the Process Value matches the Set Point. Let the system stabilise for 5 minutes.
Then continue with Auto Mode where at Data Logging, click New and then Record. Set the time
interval and check the box Auto. When the cold water outlet temperature (TIC 01) become
constant for about 15 readings, stop the recording by un-checking the box Auto and save the data.
Go to Trend, set the x-axis duration and print the graph (to PDF format).

6.1.2 Set Point Change
Conduct the experiment as in section 6.1.1 but change the Set Point value and fix the flow rate.

6.2 Experiment 2: Closed Loop Proportional-Integral (PI) Control
Run experiment by changing the I values while keeping the PB and D values constant.

6.3 Experiment 3: Closed Loop Proportional-Integral-Derivative (PID) Control
Run experiment by changing the D values while keeping the PB and I values constant.

47
Comment on the differences in terms of controller mode (P, I and D) set values, offsets, response
times and response behaviours. Figure out the system overshoot percentage and settling time.

UEMK3431 Chemical Engineering Laboratory II Exp 6: Pressure Control

48
Experiment 6
Pressure Process Control

proportional-integral-derivative (PID) controller in a pressure control loop.
To observed the different types of process pressure responses to P, PI and PID controller.

2.0 INTRODUCTION




the set point.


49


control.




integral windup.


50




offset.




51



3.0 EQUIPMENT PRESSURE CONTROL UNIT/TRAINER
The Pressure Control Unit/Trainer consists of a gas vessel connected to main reservoir vessel,
pressure sensor and electro-pneumatic proportional control valve (air supplied by a compressor).
The air pressure reading is continuously monitored by the pressure sensor with digital signal output
to the monitoring console at the computer.

continuously varied for optimum controller tuning. Demonstration of disturbance effect on process
pressure may be done with a disturbance valve to reduce the pressure of the vessel.


52

A - Safety Valve
B - Process Tank
Regulator
D - Pressure Sensor
E - Inlet Valve
F - Control Panel
G - Electro-pneumatic
Rotary Actuator with
Positioner (proportional
valve)
H - Reservoir Tank
I - Disturbance Valve

1. Read and understand the theory of pressure process control.
2. Read and understand the equipment used in the experiment (pressure control unit).

1. Ensure that the inlet valve (E) is in fully closed position.
2. Ensure that the disturbance valve (I) is in fully closed position.


53
main power supply.
3. Release all the pressure from both the Process Tank (B) and Reservoir Tank (H) by using the
Safety Valve (A) or Disturbance Valve (I).

Do not apply pressure more than 0.4 MPa to the electro-pneumatic proportional valve and the
system tanks.

6.0 EXPERIMENTS
Conduct the experiment at closed loop control option where the controller under an idle mode
and set value is between 1.5 to 2.5 bar.

Reminder:
Click the Start button and save the file. Open the inlet valve E to allow the compressed air to flow
into the process tank. Allow the system to reach steady state (where the response has stabilised).
Press Alt + Print Screen button on the computer keyboard and paste the graph in Paint or WordPad.
Press the Stop button and close the inlet valve E.

Input the set point. Repeat the experiment with different P values (1 to 100) and different set points.

Run the experiment by introducing different I value (0.05 to 2).

Run the experiment by introducing different D value (0.05 to 2). Adjust all the three parameters to

54
achieve the best system response. The control system must be able to eliminate any offset.

7.0 RESULTS ANALYSIS AND DISCUSSIONS
Discuss all your results.
UEMK3431 Chemical Engineering Laboratory II Exp 7: Flow Control

55
Experiment 7
Flow Process Control

proportional-integral-derivative (PID) controller in a flow control loop.
To observed the different types of process flow rate responses to P, PI and PID controller.

2.0 INTRODUCTION




the set point.


56


control.




integral windup.


57




offset.




58



3.0 EQUIPMENT FLOW CONTROL UNIT/TRAINER
The Flow Control Unit/Trainer consists of a process vessel connected to a main reservoir with
water pump, flow sensor and electro-pneumatic proportional control valve (air supplied by a
compressor). The liquid flow rate is monitored by the flow sensor with digital signal output to the
monitoring console at the computer.

continuously varied for optimum controller tuning. Demonstration of disturbance effect on process
flow may be done with a bypass valve to induce leakages in the process flow.


59

A - Process Tank Level
Indicator
B - Process Tank
Regulator
D - Flow Sensor
E - Water Pump
F - Control Panel
G - Electro-pneumatic Rotary
Actuator with Positioner
(proportional valve)
H - Reservoir Tank
I - Bypass / Disturbance
Valve
Figure 3.1: Flow Control Unit / Trainer

1. Read and understand the theory of flow process control.
2. Read and understand the equipment used in the experiment (flow control unit).

1. Fill the reservoir tank (H) with water to at least 3/4 of its maximum height.

1. Switch off the water pump (E).

60
main power supply.

Do not switch on the water pump if there is no water in the reservoir tank or the water level is
low.
Do not apply pressure for more than 0.4 MPa to the electro-pneumatic proportional valve.

6.0 EXPERIMENTS
Run the experiment with open loop control option. Input a set value and determine the maximum
flow rate (current value). Once the current value stabilise, press the Stop button. Then select the
closed loop control tab. Input the set value (80% of the maximum flow rate). Leave the PID in
an idle mode.

Run the experiment with different P values (1 to 100).

Run the experiment with different I value (0.05 to 2).

Run the experiment with different D value (0.05 to 2). Adjust all the three parameters to achieve the
best system response.


UEMK3431 Chemical Engineering Laboratory II Exp 8: Disc Bowl Centrifuge

61
Experiment 8
Disc Bowl Centrifuge

To understand disc bowl centrifuge working principle.
To demonstrate the separation of heavy phase liquid.
To demonstrate the effect of product type as throughput.
To calculate the separation efficiency.

2.0 INTRODUCTION
Centrifugal separators are used to separate solids from liquid or liquid from liquid using the
principle of centrifugal force. Liquid-liquid centrifuge separates two liquids of different densities
by spinning at relatively high speeds. Separation occurs as the heavy phase liquid experiences a
higher magnitude of centrifugal force causing it to settle on the outer collecting ring while the
lighter phase liquid is collected on the inner collecting ring.

There are two main types of centrifuge: tube bowl centrifuge and disc bowl centrifuge. Both can be
used to separate either solids from liquids or two liquids of different density. The tube bowl is
simply a tube rotated about its axis; the liquids are separate as they flow along the centrifuge or the
solids are thrown towards the wall. Overflow dams at the outlet end allow the two phases to be
collected separately.

For disc bowl centrifuge, the feed is admitted near the base and passes up through holes in the disc
(which are actually inverted cones). The discs are about 5 mm apart. The solids do not have to
travel far before hitting a disc and effectively being separated. Solids then continue to move
outwards and are either removed manually or through nozzles on the periphery as concentrated
slurry. Disc centrifuges range from 10 cm to 75 cm in diameter, spin speeds are in the 1000's or
rpm range.

2.1 Operating Equations for Tube Bowl Centrifuge
The radial velocity, u
r
of the denser droplets or the particles is given by:

( )
2
2 1
2
18
d
r
u
r

= (1)

where = rotational speed of centrifuge

The liquid layer thickness is small compared to the tube diameter, hence we can treat the radius of
rotation as a constant r . This gives the distance traveled in the residence time t
res
as

62
( )
res res r
t d
r
t u
2
2 1
2
18

= (2)

If the feed is homogeneous and the distance moved is equal to half the total thickness of the liquid
layer, then half the particles with diameter d will be collected. In this case d = d
50
(this only applies
if the concentration of one phase in the other is very small), thus

2
1 2
r r
t u
res r
= (3)

where r
1
= radii of the inner overflow dams
r
2
= radii of the outer overflow dams

In order to compare centrifuges of different design it is convenient to use a relationship which links
the throughput with a term which accounts for the nature of the materials and one which accounts
for the physical design of the machine.

Q
V
t
res
= (4)

where V = volumetric holdup
Q = volumetric throughput

( )
( )
( )
( )
=
= =
50
2 1
2 2
50 2 1
1 2
2 1
2 2
50
2
18
2
9
t
res
u
r r g
r V d g
r r
V r d
t
V
Q

(5)

where u
t
= terminal velocity under gravity of the d
50
particle
=
( )
2 1
2
r r g
r V

is a characteristic of the centrifuge design only and is equal to the area of gravitational settler
required to do the same duty. For scale up on the same duty

2
2
1
1
Q Q
(6)

Values of are given by manufacturers.

63
2.2 Operating Equations for Disc Bowl Centrifuge

( )
=
tan 3
2
2 3
1
3
2
g
r r n
(4)

where r
1
= inner radii of the disc stack
r
2
= outer radii of the disc stack
n = number of spaces between the discs
= cone half-angle

3.0 EQUIPMENT DISC BOWL CENTRIFUGE
The disc bowl centrifuge unit is designed to demonstrate the separation of a heavy phase liquid
using the principle of centrifugal force. This is a bench top unit comprises of an epoxy coated
frame, feed reservoir, collecting vessels, variable speed motor, feed system and control panel
mounted on the stainless steel frame.

The throughput of the feed system is at least 150 LPH. The speed of the motor can be varied from
8500 to 12000 rpm using an electronic speed controller.

Figure 3.1: Disc Bowl Centrifuge

Disc rpm
Meter
Main Power
Switch
ON/OFF
Frequency
Inverter
Mixing
Tank
Liquid
Collecting
Outlet
Disc Bowl
AC Motor

64

Figure 3.2: Disc Bowl Centrifuge Setup Components

1. Read and understand the theory of centrifugation.
2. Read and understand the equipment used in the experiment (disc bowl centrifuge).
2 L beaker 1
1 L beaker 4
Measuring Cylinder 500 mL 2
Weighting scale
Water and cooking oil


65
1. Place the apparatus on a level table.
2. Connect the 3-pin plug to main power supply. Turn on the power supply and main power
switch at the front of the control panel.
3. Press the Run green button on the frequency inverter. Test run the motor by adjusting the
turning knob on the frequency inverter to around 10 Hz. Ensure the motor is running.
4. Check the disc rpm meter and ensure that there is reading shown in the meter when the motor
is running.
5. The apparatus is ready to use if all the parts and components are working well.

4.3 Cleaning Procedures
1. Remove the mixing tank, liquid collecting outlet tray and the disc bowl.
2. Clean it with cleaning detergent and warm water.
3. Wipe all the parts and dry them.
4. Place all the parts back to it original position.
5. Fill the mixing tank with 3 - 4 litres of hot water.
6. Run the unit by setting the frequency to about 20 Hz.
7. When all the water is drained out, switch off the machine.

Do not use the apparatus for solid-liquid separation.
Do not attempt to change the setting of the speed meter and frequency inverter.
No body part should be inserted to the belt pulley system when the motor is running.
Do not remove the liquid collecting outlet tray when the motor is running.
Be aware of the slipping hazard when handling cooking oil. Avoid oil leaking and spilling on
the floor and working surfaces.
Wear gloves when cleaning the solution container.


66
6.0 EXPERIMENTS
6.1 Experiment 1A: Investigate the Effect of Frequency on Centrifuge Separation
Conduct the experiment with two different solutions at 4 different frequencies (max at 30 Hz).

Reminder:
Mix both solutions and determine the density before separation. Allow the apparatus to run for 3
minutes then record down the speed of the bowl.

6.2 Experiment 1B: Investigate the Effect of Density on Centrifuge Separation
By using the same setup as Experiment 1A, repeat the experiment using different ratio (mixture
with different density).

6.3 Experiment 2: Density Determination
Determine the density of the test fluid (take note of the unit used).

1. How does the speed of the bowl affect the separation efficiency?
2. Can we separate two solutions with densities near to each other using a disc bowl centrifuge?
Why?
3. Is it possible to estimate the separation efficiency using the data you obtained in the
experiment? If Yes, show your estimations. If No, explain why it is not possible.
4. As the proportion of water to oil changes, explain how does this affects the separation
efficiency.

UEMK3431 Chemical Engineering Laboratory II Exp 9: Fluid Mixing

67
Experiment 9
Fluid Mixing

To study the mixing and flow pattern in agitation process
To determine the speed characteristic and Power/Reynolds numbers for different types of
impellers.
To determine the mixing characteristic and Power/Reynolds numbers for different types of
liquid.

2.0 INTRODUCTION
Mixing is the random distribution of particles in separate phases, into and through one another.
Mixing also defined as reduction of inhomogeneity such as concentration, temperature and phase to
obtain the end result.

Generally in the industry, fluid mixing operations are carried out in batch and are often associated
with other processes such as separations, absorptions and chemical reactions. There are different
type of mixing mechanisms depending on the degree of mixing needed and the nature of material
used. The common mixing mechanisms include dispersion, molecular diffusion, eddy diffusion,
convection and Taylor dispersion.

Dispersion (also known as diffusion) is the act of spreading out of compounds within other
compounds.
Molecular diffusion is defined as the diffusion caused by relative molecular motion, and is
characterised by the molecular diffusivity.
Eddy diffusion or turbulent diffusion is diffusion caused by turbulent flows where eddies
created by movement of large groups of molecules take place, and is characterised by the
turbulent diffusivity.
The convection mechanism, also bulk diffusion is the dispersion caused by bulk motion of
molecules.
Taylor dispersion is related and slightly similar to convection, where dispersion is created
by a mean velocity gradient.

2.1 Theory
The mixing of liquid are carried out for several reasons:
to provide suspension of solid particles (solid -liquid dispersion)
to dissolve gas in small bubbles (gas-liquid dispersion)
to blend miscible liquids (blending)

68
to disperse other immiscible liquid (immiscible liquid-liquid dispersion)
to provide and promote heat transfer to another medium

The liquid mixers are differentiated based on several factors:
The process operation is either a batch or continuous process.
The degree of mixing required. This determines the size, power and capability of the
mixing equipment.
The nature of the process such as miscibility of solutions, preparation of liquid and the
liquids physical properties such as viscosity and acidity.

2.2 Stirred / Agitation Vessels
There are few ways to perform mixing in vessels. Most mixers contain an agitator to produce better
mixing; mechanical agitation, jets and gas sparging are often used. The different mixer geometries
differ with the variety of processing objectives, needs and application, depending on the capacity of
tank, properties of fluid and the degree of mixing required.

The mixing in an agitated vessel can be accomplished in either a continuous, batch or fed-batch
mode. Mixing can be done under two main flow conditions, i.e. in laminar flow or turbulent flow,
depending on the impeller Reynolds number. For process with laminar flow, the Reynolds number
is less than 10, while fully turbulent conditions occur at Reynolds number higher than 104.

2.3 Agitators / Impellers
Agitator will create a certain flow pattern in the mixer vessel. The flow pattern is highly influential
over the mixing process. The impeller/agitator can be classified into 2 types according to the
direction of flow generated.

The axial flow impellers, including propellers, pitched blade turbines (PBT) and hydrofoils,
generate flow currents that are parallel to the axis of impeller shaft, as a single stage. It is usually
used for blending, solids suspension, solids incorporation or draw down, gas inducement and heat
transfer.

Figure 2.1: Axial Flow Impellers


69
The radial flow impellers such as flat-blade impeller, disk turbine and hollow-blade turbine create
flow in radial path, producing circulating loops above and below the impellers. It is usually used
for low to medium viscosity fluids. These impellers provide higher shear and turbulence levels
with lower pumping compared to the axial flow impellers. Thus, they are most effective in gas-
liquid and liquid-liquid dispersion compared to other single or multiple phase mixing duties.

Figure 2.2: Radial Flow Impellers

Impellers cause liquid in the vessel to circulate throughout and end at its starting point. These flow
patterns difference cause variations in energy dissipation rate and shear rate distribution within the
vessel. For example, the axial flow impellers creates higher efficiency in liquid blending through
the single circulation loop, while the radial flow impellers is better for dispersion of gas bubbles
with dual circulation loops.

A propeller is a high speed impeller with an axial flow. It is more effective in creating persistence
current flow, especially when operating in big tanks. A turbine impeller, also known as paddles,
pushes the liquid in circles with no vertical motion involved. This creates flow current that travels
towards the vessel wall and then downwards or upwards along the wall.

Figure 2.3: Agitator Arrangements and Flow Patterns


70
2.4 Agitation Power Consumption
The agitator is driven by the shaft power, which can be estimated by the following equation. The
energy supplied to the fluid by agitation system is eventually dissipated as heat.

c b
p
K N Fr Re = (1)

where N
p
= power number =
3 5
N D
P

P = shaft power, W
D = diameter of agitator impeller, m
N = speed of agitator, rps
= liquid density, kg/m
3

Re = Reynold number =
N D
2

= liquid viscosity, Ns/m
2

Fr = Froude number =
g
DN
2

K = constant (depends on agitator type, size & tank geometry)
g = gravity acceleration, m/s
2

The power number, N
p
is also a function of impeller blade width, number of blades, blade angel,
baffle configuration & impeller elevation. Figure 2.4 and 2.5 are the power curves for single
propellers and turbine impellers that can be used to determine the respective power number. Hence,
functionality between N
p
and Re differs accordingly.

Figure 2.4: Power Correlation for Single Three Bladed Propellers Baffled


71
In laminar flow regime (Re < 10), the N
p
value is inversely proportional to Re and power depends
significantly on viscosity. In turbulent regime (Re > 10000), N
p
value is constant and independent
of liquid viscosity. In transitional regime (10 < Re < 10000), N
p
value only changes slightly.

Figure 2.5: Power Correlation for Baffled Turbine Impellers, for Tank with 4 Baffles

Density of a mixture may be computed by addition of component densities:

...
2 2 1 1
+ + = V V
m
(2)

where V
n
is the volume fraction of the components.

The viscosity of a mixture may be computed from the viscosities of the ingredients using the
following equations for baffled & unbaffled mixers:

Baffled:
2 2 1 1
V V
m
+ =

Unbaffled:
[ ]
|
|
.
|
\
|
+
+
=
2 1 1
2 2
5 . 1 1

V
V
m m

3.0 EQUIPMENT FLUID MIXING APPARATUS
The Fluid Mixing Apparatus consists of a plexiglass cylindrical mixing vessel mounted on an
epoxy coated mild steel framework. The mixing vessel incorporates a drain tap and can be
completely removable to facilitate cleaning/flushing purposes.


72
An AC motor with gearbox is used to drive the impellers. The speed of the motor can be varied
using a solid state speed controller. The speed controller gives a direct reading of the drive shaft
speed in Hertz. A load cell is attached to the motor to measure the torque reading, which is shown
digitally on a digital torque meter.

Control panel is mounted next to the plexiglass mixing vessel. The meter, controller and other
electrical components are placed on the control panel. AC circuit breaker is provided as a safety
feature.

A total of six impellers are available for experimental studies. These impellers can be easily fitted
to the drive shaft by clamping them to the locking collar.

Figure 3.1: Fluid Mixing Apparatus
A - Motor Shaft
B - Motor Supporting Plate
C - Product Tank
D - Main ON/OFF Switch
E - Digital Torque Meter
F - Motor Speed Controller
with digital display
G - Control Panel
H - Geared Motor
I - Agitator Shaft

Useful Information and Equation:
Gearbox ratio = 5
Motor Maximum Speed = 2710 rpm
Motor Speed (rps) =
60
Speed Max Motor
50
Frequency Current

Actual Speed (rps) =
ratio box gear
(rps) Speed Motor

Power, P = torque (Nm) speed (rps)


73
1. Read and understand the theory of fluid mixing.
2. Read and understand the equipment used in the experiment (fluid mixing apparatus).
Different agitator shapes / types
Measuring tape / ruler
15 L of water
15 L of cooking oil

Ensure the main power supply is OFF when fitting the agitator.
Ensure the set screw at the agitator shaft is fully tightened before starting the experiment.
Do not touch any rotating parts of the apparatus when running the experiment.
Switch OFF the apparatus immediately if there is water leakage.
Stop the motor if the water is split out from the product tank.
Do not impact the load cell.
Do not change the setting of the digital meter and motor controller.

6.0 EXPERIMENTS
6.1 Experiment 1: Investigate the Effect of Agitator Frequencies on Mixing
Run the experiment with two different test fluids at vary frequencies value.

Reminder:
Fill the product tank (C) to 15 cm height with test fluid. Tare zero the digital torque meter (E) by
pressing the UP soft button. Tare zero the Max and Min value by pressing the MAX/MIN soft
button for about 2 second respectively.
Press on the MAX/MIN soft button and record the maximum and minimum torque reading.
(Reminder: You must always tare zero the max/min reading before recording the maximum and
minimum torque reading to remove transient reading when the motor start-up.)


74
6.2 Experiment 2: Investigate the Effect of Impeller Shapes on Mixing
Repeat the experiment with different agitators for water and cooking oil.



75
Experiment 10
Fluidised Bed

To determine the pressure drop across fluidised bed.
To verify the Carman-Kozeny equation.
To observed the differences between particulate and aggregative fluidisation.

2.0 INTRODUCTION
Fluidisation is a process in which solid particles or granular materials are transformed from static
solid-like state into dynamic fluid-like state through suspension in a gas or liquid. This is
accomplished by introducing a gas or liquid flow through a bed of solid particles from the bottom.
The fluid will progress upwards through the bed via empty spaces between particles.

There exist a relationship between the bed pressure drop and the fluid velocity, U. The bed
pressure drop increases as the velocity increases. This is partly due to frictional forces between the
moving fluid and the solid particles. With higher velocities, the frictional resistance becomes
greater and hence the bed pressure drop increases.

The stages of fluidised particles from fixed bed to fluidized bed as velocities increases are shown in
Figure 2.1. As gas velocity increases, the fluidisation of sand particles become more aggressive
and it goes through different stages from incipient (minimum), particulate (smooth), aggregative
(bubbling), slugging to lean phase with pneumatic transport.

Figure 2.1: Various Region of Contacting of a Batch of Solids by fluid and Gas

gas or liquid
(low velocity)
liquid gas or liquid
fixed
bed
incipient or
minimum
fluidisation
gas gas gas or liquid
(high velocity)
particulate
or smooth
fluidisation
aggregative
or bubbling
fluidisation
slugging
lean phase
fluidisation
with pneumatic
transport


76
For fluidisation to occur, the resistance of moving gas or liquid needs to exceed the weight of solid
particle. As the gas or liquid passes upwards through bed of solids at low flow rate, it is simply
percolates through void spaces between stationary particles. Hence, the separation of particles is
constant, forming a fixed bed region. In this region, the pressure drop across bed is directly
proportional to the velocity.

At higher velocity, a point is achieved where total frictional resistance is equal to apparent weight
of particles in bed. The separation of particles increases creating a minimum fluidising velocity
point. A fluidised bed region is then formed where the pressure drop becomes constant.

2.1 Theory
2.1.1 Fixed and Fluidised Bed of Water System
The fixed and fluidised bed for a water system is generally characterised by the regular expansion
of the bed as the velocity increases from the minimum fluidisation velocity to the terminal failing
velocity of the particles. The system is hydrodynamic. In fluidised bed the particles undergo no
net movement and are maintained in suspension by the upward flow of water. A water system
exhibit particulate fluidisation, the only important exceptions being those composed of fine
particles of high density.

2.1.2 Fixed and Fluidised Bed of Air System
Fixed and fluidised bed for an air system is considerably more complex than a water system. It
exhibits a gradual from fixed bed to fluidised bed followed by particle transport, without a series of
transition regions. The bed expansion and pressure drop is close to the values calculated for ideal
systems.

As air velocity increases, the circuit tends to go through various stages as below:
Fixed bed in which the particles remain in contact with one another and the structure of the bed
remains stable until the velocity is increased to the point where the pressure drop is equal to the
weight per unit area of the particles.
Particulate and regular predictable expansion over a limited range of gas velocities.
A bubbling region characterised by a high proportion of the gas passing through the bed as
bubbles which cause rapid mixing in the dense particulate phase.
A turbulent chaotic region in which the gas bubbles tend to coalesce and lose their identity.
A region where dominant pattern is one of the vertically upward transport of particle,
essentially in air circuit. This condition sometimes referred to as fast fluidisation, which lies
outside the range of true fluidisation.

2.1.3 General Expressions for Flow through Beds in Term of Carman-Kozeny Equation
General expressions for pressure drop and mean velocity for flow through packing in term of
voidage and specific surface is given by


77

( )
t
t
l
P d
u

=
32
2
(1)

where u = mean velocity of the tube
= viscosity of the fluid
d
t
= diameter of the tube
l
t
= length of the tube

If flow conditions within the bed are streamline, the relation between fluid velocity u
c
, pressure
drop (-P) and voidage e is given by (for fixed bed of spherical particles of diameter d),

( )
|
|
.
|
\
|
|
|
.
|
\
|
=
l
Pd
e
e
u
c
2
2
3
1
0055 . 0 (2)

For a fluidised bed, the buoyant weight of the particles is counterbalanced by the frictional drag.
So Eq. (2) becomes

|
|
.
|
\
|
|
|
.
|
\
|
g d
e
e
u
s
c
) (
1
0055 . 0
2 3
(3)

where g = acceleration due to gravity

s
= density of particles
= density of fluid
l
t
= length of the tube

The Carman- Kozeny equation is not suitable when the flow regime is at the point of incipient
fluidisation. Pressure gradient for laminar (Re < 10) and turbulent (Re > 2000) flows through a
packed bed of mono-sized of spherical particle with diameter d
p
, is expressed in the Ergun equation:

( ) ( ) ( )
3
2
3
2
2
1
75 . 1
1
150
=

p
f
p
d
U
d
U
H
P
(4)

where
( )
H
P
= pressure gradient
U = fluid velocity
= voidage
d
p
= diameter of particle

f
= density of fluid


78

Ergun equation is a combination of laminar and turbulent component of pressure gradient. Under
laminar flow, the first term of the equation dominate and reduced to the Carmen-Kozeny equation.
Due to the differences in shapes and packing of the particles, the constant is changed from 180 to
150. The second term dominates when the flow is turbulent. The pressure gradient increases
linearly with superficial fluid velocity in laminar flow and is independent of fluid density.

The minimum fluidised velocity, U
mf
is required in order for fluidisation to occurred. U
mf
can be
obtained by plotting the graph of bed pressure drop, P versus fluid velocity, U as shown in Figure
2.2, which is represented by point A. OA is the fixed region whereas BC is the fluidised bed region.

Figure 2.2: Pressure Drop versus Fluid Velocity in Fixed and Fluidised Beds

3.0 EQUIPMENT FIXED AND FLUIDISED BED APPARATUS
The fixed and fluidised bed apparatus consists of two cylindrical acrylic columns, one for water
circuit (right) and the other one for air circuit (left), mounted on epoxy coated mild-steel frame.
The two circuits are independently controlled and can be operated separately or together according
to the experiment requirements.

Water is circulated from a sump tank through a digital flow meter and control valve to the column
by a water pump. Two valves are provided in the water circuit, i.e. a control valve to control the
water flow rate and a bypass valve to prevent overloading the water pump. The water is returned to
the sump tank via an overflow.

A diaphragm air pump is used to supply air to the second column. A control valve is provided to
control the air flow rate before entering the column. Each column has tapping points and a digital
manometer for measurement of the bed pressure drop. The column Inner Diameter is 46 mm.

Bed Pressure
Drop, P
Fluid Velocity, U
U
mf

A
B
C
O

79

Figure 3.1: Fixed and Fluidised Bed Apparatus

1. Read and understand the theory of fluidised bed.
2. Read and understand the equipment used in the experiment (fixed and fluidised bed apparatus).
Air compressor
Test materials: sand, carbon grain, acrylic

4.2 Changing Test Material and Cleaning Procedures
1. Switch OFF the main power supply of the apparatus.
2. Release the quick release coupling of the column.
3. Loosen the upper and lower removable coupling. (Note: Be careful with the test material
which may leak out from the column.)
Main ON/OFF
Switch
Digital Water
Flow Meter
Water Flow
Control Valve
Digital Pressure
Drop Meter
(water column)
Water Bypass
Valve
Water
Column
Air Flow
Control Valve
Water
Pump
Digital Pressure
Drop Meter
(air column)
Digital Air
Flow Meter
Air
Column
Upper Removable Coupling
Lower Removable Coupling

80
4. Clean and wash the column.
5. Place the column back to its original position and tighten the lower removable coupling.
6. Fill the column with another test material.
7. Tighten the upper removable coupling.
8. Connect the quick releasing coupling back to the pressure points.

Do not fill the test material more than half the column height.
Do not start the water pump if there is no water in the water tank (should fill up to height).
Tighten the upper removable coupling and the lower removable coupling and ensure that there
is no water or air leakage.
Ensure the quick released couplings for the pressure drop points are connected properly for both
of the water and air column.
Do not allow the air blower and water pump to run for long period of time if all the valves are
fully closed.
Do not attempt to change the setting of the digital meters.

6.0 EXPERIMENT
6.1 Experiment 1A: Determine the Pressure Drop across Fluidised Bed in Water System
Run the experiment with at least Five different water flow rate.
Reminder:
Set the water flow rate to 0.1 LPM by regulating the water flow control valve and the water bypass
valve. Keep an eye on the digital water flow meter. Drain off the water from the column after the
experiment.

6.2 Experiment 1B: Investigate the Pressure Drop across Fluidised Bed for Different
Materials in Water System
By using the same setup as Experiment 1A, repeat the experiment with different test material (refer
to Section 4.2 for procedures to change the test material).
Reminder:
The height of the test material in the column must be the same as the previous experiment.


81
6.3 Experiment 2A: Determine the Pressure Drop across Fluidised Bed in Air System
Run the experiment with different air flow rate until few sets of constant pressure drop readings are
taken.

6.4 Experiment 2B: Investigate the Pressure Drop across Fluidised Bed for Different
Materials in Air System
By using the same setup as Experiment 2A, repeat the experiment with different test material (refer
to Section 4.2 for procedures to change the test material).
Reminder:
The height of the test material in the column must be the same as the previous experiment.



82
Experiment 11

Serial Dilution-Agar Plate:
Quantitative Measurement of Viable Cells


To understand and learn serial dilutions and plating techniques in estimating the number of
microorganism quantitatively
To determine the number of viable cells per unit volume in the original culture

2.0 INTRODUCTION

Studies involving the analysis of materials such as food, water, milk, and, in some cases, air require
quantitative enumeration of microorganism in the substances, in order to establish viable cell count.
Scientists devise various methods to determine the number of microorganisms that are present in a
given population. This can be accomplished by using the spectrophotometer to measure the optical
density of the population, by directly counting the microorganisms using a haemocytometer, or by
serial diluting the bacteria and plating the diluted bacteria on media that supports the growth of the
micro-organisms. The major disadvantage of direct microscopic counts technique is that the total
count includes dead as well as living cells. On the other hand, the spread-plate method as
illustrated in Figure 1, is somewhat more time consuming, but provides statistically accurate and
repeatable results. This method is also the ideal method for enumerating microorganisms in a given
population because it only identifies the living organisms in that population.

Figure 1: Spread-plate technique.

Briefly, this method involves serial dilution of a bacterial suspension in sterile water blanks, which
serve as a diluent of known volume (Figure 2). Once diluted, the suspensions are pipette onto the
surface of the agar plate, as illustrated in Figure 1. The process is followed by gently spread the
liquid culture onto the surface of the agar, by moving the spreader in a circular manner while
rotating the plate. This will ensure an even distribution of bacteria. When done, put the agar plates
in a 37
o
C incubator or another suitable warm place (such as on top of the fridge). Formation of
bacteria colony could be observed in 24 to 48 hours.


83

Figure 2: Ten-fold serial dilution.

In the present experiment, we will be using serial dilutions, plating and counting of viable
Saccharomyces cerevisae to determine the number of yeast in a given sample. To this end we will
make serial dilutions of a solution containing an unknown number of yeast, plate this yeast and
determine the total number of yeast in the original solution by counting the number of colony
forming units and comparing them to the dilution factor. In this experiment, ten-fold serial
dilutions are used in titrations of the yeast suspension. They are carried out in small sterile test
tubes. After incubation process, each colony forming unit on the agar plate represents a bacterium
that was present in the diluted sample. The numbers of colony forming units (CFUs) are divided
by the product of the dilution factor and the volume of the plated diluted suspension to determine
the number of bacteria per mL that were present in the original solution.

3.0 METHODOLOGY

3.1 Equipments and Materials
Tubes containing 1 ml of sterile 0.9% NaCl (sterile saline; 10 tubes per group), YPD agar plates (3
per dilution), sterile micro-pipette tips (1 mL), Bunsen burner, glass spreader, parafilm strip,
incubator (37
o
C), sterile sticks (2), micropipettor, 70% alcohol

This class will only work with standard laboratory strains of Saccharomyces cerevisae.
Nevertheless, we shall consider all cultures to be potential pathogens and will rigorously adhere to
the following precautions:

84
No eating, drinking or smoking is allowed in the laboratory.
Do no pipette cell suspensions by mouth.
Notify the instructor if you have an open cut or burn.
Notify the instructor of any spilled cultures for proper decontamination process.
After each lab period, wipe your benchtop down with 70% alcohol or disinfectant and wash
your hands.
Cultures are not allowed to be poured into the sink or thrown in the ordinary trash.
Agar plates are to be placed in the designated biohazard plastic bag for decontamination
process.
Flasks, tubes, micropipette tips and bottles are to be placed in the autoclaving basket
provided for decontamination process.
Bunsen burners
The Bunsen burner possess flammability hazard when applied in conjunction with ethanol. Hence,
(i) turn off Bunsen burner when you are not using it; (ii) if your hair is long, tie it up during the lab;
(iii) keep your ethanol bottle away from the flame and cover the bottle if you are not using it.

3.3 Experimental Procedures
Experimental flowchart is illustrated in Figure 3.

Figure 3: Experimental works.

85

DAY 1
Set up 10 sterilized glass test tubes in a rack and label each tube clearly (10
-1
, 10
-2
, 10
-3
, 10
-4
, 10
-5
,
10
-6
, 10
-7
,10
-8
, 10
-9
), to indicate the dilution of its contents after the ten-fold serial dilution has been
carried out.
Label 5 agar plates as follows: 10
-4
, 10
-5
, 10
-6
, 10
-7
, 10
-8

Use a 1-mL STERILE micropipette tip to dispense 900 L of the sterile NaCl (0.9%w/v) to all the
labeled sterile tubes.
Use a micropipette to transfer 1 mL of the sample (yeast suspension) to the first tube. Mix the
solution properly. This is the first ten-fold dilution.
Use a micropipette with new sterile tip to carry out a second ten-fold dilution.
Continue the series of ten-fold dilutions until the last tube.
Use a sterile pipette to transfer 1 ml of the suspension from tube 10
-4
and squirt it onto the surface
of the agar plate labeled 10
-4
. Repeat the steps until the tube 10
-8
, as follow.

Spread 1 mL from culture tube 10
-5
onto plate 10
-5

-6
onto plate 10
-6

-7
onto plate 10
-7

-8
onto plate 10
-8

Sterilize the bacterial spreader by dipping it into a beaker of 70% alcohol. Remove and shake off
the excess. Carefully run the spreader through the flame of a Bunsen burner and allow the alcohol
to burn off. Cool the spreader by holding it against the condensation on the inside of the petri dish
lid.

Gently spread the liquid culture onto the surface of the agar by moving the spreader in a circular
manner while rotating the plate. This will ensure an even distribution of bacteria.

Allow plates to absorb the cultures, then turn plates upside-down and incubate overnight at 37
o
C.

3.4 Results Analysis and Discussion

Discuss all your results. Answer all the questions.

DAY 2

Count only plates containing between 30 and 300 colonies.

Any plate which has more than 300 colonies is designated as "too numerous to count TNTC".
Plates with fewer than 30 colonies are designated as too few to count TFTC to be statistically
acceptable.


86
Record your observations and calculated cell counts per mL of sample. Since the dilutions plated
are replicates of each other, determine the average of the duplicate cell counts per mL of sample.

The number of organisms per mL of original culture is calculated by multiplying the number of
colonies counted by the dilution factor.


1. Estimate the number of viable cells per mL of original sample.
2. List TWO major disadvantages of microbial counts performed by the serial dilution-agar plate
procedures.
3. Distinguish between dilution and dilution factor.
4. If 0.1 mL of a 1 X 10
-6
dilution plate contains 56 colonies, calculate the number of cells per mL
of original culture.
5. How would you record your observation of a plate containing 305 colonies? And, a plate with
15 colonies?


87
Experiment 12

Determination of specific growth rate ( ) of
Escherichia coli


To understand the population growth dynamics of bacterial cultures
To determine the generation time of a bacterial culture from the bacterial growth curve.
To determine the coefficient of biomass yield (Y
x/s
) of E. coli cultivated in LB-medium
containing different initial concentration of glucose.

2.0 INTRODUCTION

Bacterial Growth Phase

Bacterial population growth studies require inoculation of viable cells into a sterile broth medium
and incubation of the culture under optimum temperature, pH, and gaseous conditions. Under these
optimal and defined conditions, the cells will reproduce rapidly, consume the nutrients from
medium and convert them into biological compounds. Composition of the culture medium, the
biomass concentration, and the metabolite concentration are generally changed constantly as a
result of the metabolism of the cells.

The stages of a typical cell growth curve (Figure 1) are:

1. Lag phase: This is the time of adaptation of cell to the new environment. This phase can
be very short or quite lengthy, depending on the age of inoculum (active or not),
environmental and medium condition. During this phase, cell mass may increase a little,
without an obvious increase in cell number density. Although the cells are increasing in
size, there is no cell division and therefore no increase in numbers of cells could be detected.
2. Logarithmic (Exponential) phase: Once the necessary alterations are completed, the cells
move into the growth phase, which is normally known as log or exponential phase. This is
a period of rapid growth occurred, during which the cell numbers increase exponentially
with time. The cells reproduce at a uniform and rapid rate by binary fission, which doubles
regularly until a maximum number of cells is reached. The time required for the population
to double is the generation time. During exponential phase, organism is growing at a
maximum and constant specific growth rate (
max
).
3. Stationary phase: This stage occurs when (i) all the cells have stopped dividing or (ii)
when viable cells have reached equilibrium with dead cells (growth rate = death rate) or (iii)
is point where the growth rate has declined to zero. Therefore, there is no further increase
in cell number, and the population is maintained at its maximum level for a period of time.
The primary factors are (i) depletion of some essential nutrients and (ii) accumulation of
toxic products that inhibit the growth of cultures.
4. Decline or death phase: At the end of stationary phase, because of either nutrient depletion
or toxic product accumulation, the death phase begins. Often, dead cell lyse and release

88
intracellular nutrients into the medium which can be used by living organisms during
stationary phase.

Figure 1: Typical growth curve for a bacterial population cultivated under batch cultivation
mode.

Normally, construction of growth curve of microorganism requires sampling of 24-hour cultivation
process for measurement of population size at predetermined intervals during the incubation period.
However, such procedure does not lend itself to a regular laboratory session. Therefore, in the
present experiment, slight modification will be done to demonstrate only the log phase of culture.
The growth curve of log phase will be plotted for measurement of culture growth and specific
growth rate ().
Exponential Growth Model

To describe logarithmic growth, the following equation is frequently used:

(1)

where,
= apparent specific growth rate (h
-1
)
X = biomass concentration (g/L)
t = cultivatin time (h)

X
dt
dX
=

89
by splitting the variables in equation (1), we obtain:

(2)

if at time t
0
, the [biomass] in the bioreactor is X
0
, and, at time t, the [biomass] is X
t
, then, equation
(2) becomes:

(3)

Integrating both sides in equation (3) gives:-

ln Xt = ln X
0
+ (t
t
t
0
)

ln X
t
= ln X
0
+ t
t
(4)

where,
X
t
= concentration of cells after the time interval, t hours
X
o
= concentration of cells at time 0 or initial biomass concentration

Based on Equation 4, plot of the ln [Xt] versus time t should yield a straight line with the slope of
the line equal to.

Doubling Time (t
d
) and Specific Growth Rate ( )

The doubling time (t
d
) or also known as generation time is an expression commonly used by
microbiologist to describe the rate of cell growth. It represents the time taken for the cell
population to double (Figure 2).

Figure 2: Doubling time
dt dX
X

1
=
} }
=
t t
X
X
t
t
dt dX
X
0 0

1

90

The relationship between the doubling time (t
d
) and can be derived as follow. Assume that the
biomass concentration doubles from X
1
to 2 X
1
over a doubling time of t
d
(= t
2
t
1
), then the
equation (4) will become:

ln X
t
ln X
0
= t
t

ln 2 X
1
ln X
1
= t
d

3.0 METHODOLOGY

3.1 Equipments
Waterbath shaker incubator (37
o
C), Vis spectrophotometer, normal cuvettes, pre-dry cellulose
nitrate membrane filter paper (30 pieces per group), 1-mL sterile pipettes, micropipettor, Bunser
burner, beaker, 70% alcohol, vacuum filtration system.

3.2 Cultures
8- to 12- hour (log phase) LB broth culture of Escherichia coli with OD of 0.10-0.20 at 600 nm.

3.3 Media
Per designated student group: 130 mL of LB broth in a 250-mL Erlenmeyer flasks (3 flasks per
group).

d
1
1
t
X
X 2
ln =
d
t 2 ln =
2 ln
=
d
t
693 . 0
=
d
t

91
3.4 Experimental Procedures

Inoculum preparation (prepared by lab assistant)

1. Use E. coli in this experiment.
2. Inoculate 3 loops of culture from slant agar into conical flask containing 100 mL of inoculum
medium (LB medium) containing (g/L): bacto-tryptone, 10; bacto-yeast extract, 5; and NaCl,
5.
3. Adjust initial culture pH to 7.2 prior to sterilization.
4. Incubate the flask in incubator shaker at 37
o
C at 250 rpm overnight to obtain stationary phase
cells.

Fermentation Process

1. Prepare 130 mL of LB broth in a 250-mL Erlenmeyer flask (3 flasks per group). Sterile the
solution at 121
o
C for 15 min. (prepared by lab officer one day before the lab class)
2. With a sterile pipette, add approximately 5 mL of the log phase E. coli inoculum into to the
flask containing 100 mL LB broth.
3. Mix the content of the flasks properly by gentle rotation.
4. Withdraw 5 mL of culture broth from the flasks, transfer it to a sterile centrifuge tube and
label it as sample t
0
. Please refer to Section 3.5 and 3.6 for sampling and analysis of sample.
5. Incubate the remaining cultures by using a waterbath shaker incubator at 37
o
C for 250 rpm.
6. Thereafter, at each 30-minute interval, shake and aseptically transfer 5 mL aliquot of the
culture for analysis. Label each sample as to time of sampling : t
30
, t
60
, t
90
, t
120
, t
150
, t
180
, t
210
,
t
240
.

3.5 Sampling

Withdraw 5 mL of sample from the flasks at each 30-minute interval for 4 hours of cultivation
process. These samples will be used for measurements of cell concentration (in terms of OD and
dry cell weight) and glucose concentration. (Note: Store the sample at -20
o
C if you cannot carry
out the analysis at the same day of experiment)

3.6 Analytical Procedures

a) Determination of biomass concentration (OD at 600nm)

1. Put the 5 mL sample into centrifuge tube and centrifuge at 9 000 rpm for 5 min.
2. After centrifugation, discard the supernatant.
3. For the remaining cell pellet, add in same volume of distilled water (in this case, 5 mL will be
needed) and mix it in order to obtain homogenous cell suspension.
4. Centrifuge again at 9 000 rpm for 5 min, after which discard the supernatant.
5. Again, add in same volume of distilled water and mix the suspension.
6. Measure the absorbance using spectrophotometer at 600 nm by using a spectrophotometer.
7. Use distilled water as BLANK. Dilution is required if the reading of absorbance is too high
(>1.500). Absorbance for each diluted sample can be calculated as absorbance value at 600nm
(Abs600) x dilution factor.
8. Collect all the cells suspensions (include the diluted sample) for dry cell weight determination.


92
b) Determination of dry cell weight (DCW)

Determine cell concentration (in term of dry cell weight) by filtration (Figure 3) and oven drying
method. Weigh the dry weight of a 0.2 m cellulose nitrate membrane filter (Whatman). Filter the
5 mL cell sample through the pre-weighed cellulose nitrate membrane filter (Whatman) by using a
vacuum pump. Place the cell and the filter paper on a glass Petri dish. Dry the cells overnight in an
oven at 80
o
C. Measure the dry weight of filter paper with cells after cooling the filter paper in
desiccator for 5 min.

The dry cell weight (DCW) can be calculated as:

Figure 3: Vacuum filtration method


1. Plot a population curve with the dry cell weight (g/L) on the ordinate and the incubation time
on the abscissa. Describe the plot obtained.

2. Plot ln X
t
on the ordinate and the incubation time on the abscissa. From the plot, determine:
i. Initial cell concentration, X
0

ii. Specific growth rate,
iii. Maximum specific growth rate,
max

3. Determine the generation time of E. coli used in this experiment. Compare and your results
with the data obtained from the literature. Explain why do variations in generation time exist:
(a) among different species of microorganisms, and, (b) within a single microbial species.

4. Is generation time a useful parameter to indicate the types of media best suited to support the
growth of a specific organism? Explain.

(L) volume Sample
(g) paper filter dry of weight - (g) cells paper filter dry of Weight
(g/L) DCW
+
=

93
5. Plot also the graph OD versus dry cell weight for each flask. Determine the relationship
between them by calculating the slope of the straight line.

Experimental flow chart

Cell pellet
Add in 5-mL distilled water
Vortex
Read absorbance at 600nm (A
600
)
(Keep the sample for dry cell weight determination)
Vacuum filtration and drying of sample
Discard Supernatant
Centrifuge (9 000 rpm, 5 min)
Dry Cell Weight (g/L)
5-mL sample
Repeat the cell washing process twice

94
Experiment 13

Phase Determination of some polycrystalline or
powdered solid samples


To understand the principle of X-ray Diffraction
To carry out XRD analyses on polycrystalline or powdered solid samples.
To solve the complete structure of the crystalline materials.
To calculate the crystallite sizes of the major reflection planes of each sample.

2.0 INTRODUCTION

About 95% of all solid materials can be described as crystalline. When X-rays interact with
a crystalline substance (Phase), one gets a diffraction pattern. In 1919 A.W.Hull gave a paper titled,
A New Method of Chemical Analysis. Here he pointed out that .every crystalline substance
gives a pattern; the same substance always gives the same pattern; and in a mixture of substances
each produces its pattern independently of the others. The X-ray diffraction pattern of a pure
substance is, therefore, like a fingerprint of the substance.

The powder diffraction method is thus ideally suited for characterization and identification
of polycrystalline phases. Today about 50,000 inorganic and 25,000 organic single component,
crystalline phases, diffraction patterns have been collected and stored on magnetic or optical media
as standards. The main use of powder diffraction is to identify components in a sample by a
search/match procedure. Furthermore, the areas under the peak are related to the amount of each
phase present in the sample.

X-ray crystallography is a method of determining the arrangement of atoms within a crystal,
in which a beam of X-ray strikes a crystal and diffracts into many specific directions. From the
angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional
picture of the density of electron within the crystal. From this electron density, the mean positions
of the atoms in the crystal can be determined, as well as their chemical bonds, their disorder and
various other information.

This method determined the size of atoms, the lengths and types of chemical bonds, and the
atomic-scale differences among various materials, especially minerals and alloys. X-ray
crystallography is still the chief method for characterizing the atomic structure of new materials and
in discerning materials that appear similar by other experiments. X-ray crystal structures can also
account for unusual electronic or elastic properties of a material, shed light on chemical interactions
and processes, or serve as the basis for designing pharmaceuticals against diseases.


95

3.0 EQUIPMENT X-RAY DIFFRACTOMETER

The XRD-6000, an X-ray diffractometer analyze crystalline states under normal
atmospheric conditions. This method is non destructive. X-rays focused on a sample fixed on the
axis of the spectrometer (goniometer) are diffracted by the sample. The changes in the diffracted X-
ray intensities are measured, recorded and plotted against the rotation angles of the sample. The
result is referred to as the X-ray diffraction pattern of the sample. Computer analysis of the peak
positions and intensities associated with this pattern enables qualitative analysis, lattice constant
determination and/or stress determination of the sample. Qualitative analysis may be conducted on
the basis of peak height or peak area. The peak angles and profiles may be used to determine
particle diameters and degree of crystallization, and are useful in conducting precise X-ray
structural analysis.
XRD-6000


96


97


98


99


100


101


102
4.1 PROCEDURES FOR BASIC DATA PROCESSING& SEARCH/MATCH

When sample scanning is finished it will be saved in the directory and with the name, which you
already mentioned in the Gonio condition setup.
Basic process is the process in which the software will apply different processes to the raw data and
later on this data can be used for search match and for other calculations.

Click Basic Process Program as shown below.

Fig. 1

You will see the window like shown below:

Fig. 2
Now open data files by clicking XRD Data icon as shown below.


103

Fig. 3

Now you will see all the data files as shown below left side.

Double click your directory (Group) and it
will show you your files as below.

Fig. 4 Fig. 5

Now drag your file to basic process window (Fig. 2), which you have opened already. Now you
will find that window as below on the next page.

Press System error correction correction button and make it yes for standard conditions.

104

Fig. 6
Change this condition to YES

Then press GO icon in the same window on the top icon line as shown.

Fig. 7

Now you will get the following window


105

Fig. 8

Now the process is finished and you can close this window> your data is ready for database search
or for other processes. It will save all the processed files in the same directory as shown below.


106

Fig. 9

Search Match

Now after basic process you can go through the search match. Click search program as shown
below.

Fig-10

Now you will see the following window


107

Fig. 11

Now drag your data file in the above window and you will see as follows

Drag your
data file from
your data
directory
here for
search match

108

Fig-12

Now click Search and from there click Pre-Search and click ok by putting the proper
parameters or you can keep the default parameters and click search button and you will see.


109

Fig-13

Fig-14
Now again from the Search click search and you will find the following window.


110

Fig-15

Now put the proper information and press search button and you will find the data as follows.

Fig-16


You can include
elements from this
button.

You can define
proper group here.

111
Experiment 14

Physisorption analysis on some polycrystalline or
powdered solid samples

To determine the specific surface area of micro-, meso- or macro-porous types of
materials.
To study the Langmuir Isotherm of the given materials.
To learn the principles of surface area measurements by using Nitrogen Physisorption.

2.0 INTRODUCTION

BET theory aims to explain the physical adsorption (Physisorption) of gas molecules on a
solid surface and serves as the basis for an important analysis technique for the measurement of the
specific surface area of a material. In 1938, Stephen Brunauer, Paul Hugh Emmett and Edward
Teller published an article about the BET theory in a journal for the first time; BET consists of
the first initials of their family names.

The characterization of a solid provides information of three distinct but related types.
These are: chemical composition and chemical structure; texture and mechanical properties; surface
activity. By chemical composition and chemical structure, we refer to matters such as: elemental
composition; the composition, structure and proportions of individual phases which may be present;
surface composition; the nature and proportions of functional groups which may be present on the
surface.

The texture of a solid refers to its geometric structure and morphology, ranging from the
grossest macro scale down to the finest microscale. This deals with, for instance, size and shape of
individual units (for example, individual particles, pallets); pore structure; total surface area; the
way in which individual phases are arranged relative to one another. The mechanical properties
refer to those which are important to the integrity of the solid in an industrial application. This
refers to matters such as abrasion or attrition resistance, strength, and thermal shock resistance.

The characterisation of a solid in terms of its activity is obviously a quantitative measure of
the ability of a solid to carry out a particular chemical transformation under specified conditions.
Basically this will specify a quantity such as rate of reaction, or some quantity related to rate of
reaction, per unit quantity of solid. Bearing in mind that many reactions are not specific for the
formation of a particular molecular product, the specification of activity must also include product
selectivity.


112
3.0 EQUIPMENT SORPTOMATIC 1990

The Sorptomatic 1990 is a complete computerised instrument based on a static volumetric
principle to characterise solid samples using gas adsorption techniques.

The instrument being completely made of stainless steel, it can be used with a wide range of
gases (inert and corrosive) and vapour to enlarge the investigation possibilities on the solid state,
matching the increasing needs of modern research.

The Sorptomatic 1990 can perform the following techniques:

Physisorption:

The specific surface area and the pore size distribution are fundamental parameters for the
characterisation of solids. Properties such as porosity, strength, hardness, permeability, separation
selectivity, corrosion, thermal stress resistance, etc. can be directly correlated to the porous
structure of the material. These properties can be easily investigated by the Physisorption technique.

By using inert gases such as Nitrogen, it is possible to determine the specific surface and
pore size distribution of a large number of solids and powders. In case of very low specific surfaces
(non porous materials) Krypton can be easily used, while for some ultramicroporous solids, like
some zeolites, Argon physisorption is a common technique applicable by the instrument. Common
coolant for the analysis are liquid Nitrogen or Argon.

Adsorbates : Nitrogen, Argon, Krypton, Carbon dioxide, etc.
Applications : Catalysts, Active carbons, Charcoals, Pharmaceuticals, Building materials,
Cements, Glass, Soils, mineral Metal powders and sintered metals, Oxides
and salts, Adsorbents, Ceramics, Pigments.
Results : Specific surface, Meso/micropore distribution, Meso/micropore volume,
Cumulative specific surface, Cumulative pore volume.

The Sorptomatic 1990 operations are completely automated by a dedicated software for
Sorptomatic 1990 loaded on suitable PC connected via RS232 link. The dedicated MILESTONE
software for Sorptomatic 1990 generates a Digital Status Display (D.S.D. Fig. 1.2) screen on the
PC's video which shows the status of the Sorptomatic 1990 in real time and permits the user to
control and monitor all the instrument functions by clicking the mouse on the relevant option. The
user can open or close valves, outgas the system, select the pre treatment procedures, read
temperatures and pressures, start analysis, etc.


113

During or after the analysis, the software receives the experimental points from the instrument's
internal data buffer for elaboration (see "Brain").
The software lets the user select the portion of the adsorption/desorption plot to be analysed on the
screen using the mouse.

The methods available depends on the software and are easily selected from a drop down menu:

Specific surface: BET 2 parameters (standard); Dubinin Raduskevitch
Pore size distribution: BJT; Dollimore & Heal; Horwath & Kavazoe

The "brain" of the Sorptomatic 1990 is a powerful microprocessor controlling and
monitoring all the phases during both the analysis and the sample pre-treatment.
The microprocessor receives the analytical and pretreatment parameters directly from the personal
computer. Once the experiment starts the microprocessor can control the injection pressure and
volumes as a feedback of sample adsorption rate to optimise the number of equilibrium points to be
collected. The equilibrium points, the injection parameters and the saturation pressure are
continuously monitored and memorised in an internal battery back-up instrument memory so that
the Sorptomatic 1990 can take over the analysis even without the connection with the PC. If the PC
is connected it can monitor the system status, the experimental conditions, the adsorption in real
time and the sample pre treatment status.

The microprocessor approach in the Sorptomatic 1990 electronics enables unexperienced
users to perform without problems difficult experiments as Chemisorption or Krypton analyses
thanks to the A.G.I.S. technique (Automatic Gas Introduction System). A.G.I.S. is an innovative
algorithm which dramatically simplifies the choice of the correct analytical parameters.
Once the sample adsorption rate and the number of experimental points have been selected, AGIS
takes over automatically determining the correct amount of adsorbate to be injected into the sample
holder. AGIS not only optimises the inlet gas pressure but, if necessary, also modifies the dosing
piston volume so that the pressures being used are within the optimal measuring range of the
pressure transducer.


114
With one or more optional pressure transducers AGIS can operate in up to three preselected
adsorption pressure regions and one desorption range of the isotherm providing extremely high
resolution exactly where it is required. Sorptomatic 1990 unifies full automation, which means the
simplicity necessary in QC applications, and analytical reliability thus matching even the most
critical measurement requirements expected by sophisticated researchers.

Four experimental procedures are included in the software to permit the best possible match
between sample nature and analysis type. Three of these procedures have been perfected in the
Microstructure Lab to optimize analytical performance in the Physisorption on microporous,
mesoporous and low porosity (low surface area) materials.

These procedures have the advantage that they do not require experienced personnel to
obtain results.


Sorptomatic Series 1990 Procedure BET Equipment

Experiment A (Degassing)

1. Connect the stopcock to the sample tube using the springs (apply grease at the connecting
points).
2. With the stopcock CLOSED, connect the sample tube to the degassing port using the
normal degassing connector.
3. Turn ON the appropriate degassing port valve and wait for pressure indicator show lower
than 70 kPa and slowly OPEN the stopcock (up to 180 deg).
4. Turn ON the furnace from Sorptomatic Control Menu and degas for at least 30 minutes.
5. Once degassing completed, turn OFF the furnace, CLOSE the stopcock and switch OFF the
degassing port valve.
6. Remove the degassing connector and weigh the sample tube attached with spring and
CLOSED stopcock. Record as blank weight.
7. Remove the stopcock and spring.
8. Fill in the sample into sample tube (approx. 0.55g) by using funnel.
9. Connect the stopcock and springs to the sample tube and repeat step (2 to 5) and degas for
overnight (Use the Powder Degassing Valve if sample is in fine powder form).
10. Repeat step (6). Record as tube + sample weight.
11. Connect the stopcock and springs to the sample tube and transfer to the analysis port.
12. Actual sample mass = (Tube + Sample weight )- (Blank weight)

Experiment B (Blank Analysis)

1. CLOSE all the stopcocks of the samples which are currently degassing at the degassing port
and switch OFF the degassing port valve.
2. Connect the sample tube with sample which previously degassed (with stopcock CLOSED)
to the analysis port.

115
3. Place the Liquid Nitrogen Analysis Dewar below the sample tube and attach the PT100 to
the sample tube. Make sure that the gas using is GAS 2 (He
2
), otherwise apply Change Gas
Procedure.
4. Follow the step below while operating the Sorptomatic 1990 software.

Sorptomatic Control (Flow Sheet)

5. Switch ON turbo pump and click open the valve #4, #2, #1, and #8 (following sequence)
and let the piston on to the top position. Wait until the P.Equi value <0.00xx (negative value
is even better).

6. Slowly OPEN the stopcock up to 180 deg.

7. To open the previous analysis data:
Click File > New > Check Delete Ads/Des points > Update.

8. Under Sample Information tab, insert the detail of sample and name.

9. Under Acquisition Par. Tab, make sure analysis type is Ads + Des then click save.

10. Recall the analysis file saved previously, click on the top of taskbar then select File in
memory.

11. Note that the Acquisition Parameter is the one in the analysis file and click on Send to
instrument then click exit.

12. Please make sure the Liquid Nitrogen tank is filled. Place the Liquid Nitrogen Analysis
Dewar into its position and click .

13. After the Liquid Nitrogen filling complete, click on Run and select Start. Click Yes to
confirm the analysis start running.

14. After the analysis completed, End of analysis message will appear at the status bar.

15. Take out the analysis tube from the analysis port.

16. Choose Instrument 1 at the top taskbar and then click on the Acquire points from
instrument icon and save the result under same name.

17. Click YES to confirm update acquire points in memory and click Continue to save.

18. Click Run at the top taskbar and select Reset for the instrument to be standby for next
analysis.


116
Experiment C ( Sample Analysis)

1. CLOSE all the stopcocks of the samples which are currently degassing at the degassing port
and switch OFF the degassing port valve.
2. Connect the sample tube with sample which previously degassed (with stopcock CLOSED)
to the analysis port.
3. Place the Liquid Nitrogen Analysis Dewar below the sample tube and attach the PT100 to
the sample tube. Make sure that the gas using is GAS 1 (N
2
), otherwise apply Change Gas
Procedure.
4. Follow the step below while operating the Sorptomatic 1990 software.
5. Repeat step (5 to 18).

Change Gas Procedure

1. Install the sample tube (with or without sample) to the analysis port with stopcock
CLOSED.
2. Click Other at the top of taskbar and choose Change gas the follow the instruction on
screen:
a. Click OK when ready with a CLOSED sample burette.
b. Close inlet reducer (the left valve with GAS tagged) then click OK.
c. Change gas with selector valve (GAS 1/GAS 2) then click OK.
d. Please open inlet reducer (appr.-25 kPA) then click OK.
e. Change gas complete, click OK.
f. Please verify pressure (turn the inlet reducer valve to >50 kPa) then click OK.

Remark: * GAS 1 is nitrogen using for sample analysis.
* GAS 2 is helium using for blank analysis.


117



118
Experiment 15
Determination Of The Optimum Conditions For Pure Metal
Oxide Used In A Chemical Reaction

To determine the optimum reduction temperature in the pretreatment of pure metal oxide.
To determine the activation reduction and desorption energies.
To calculate the total amount of desorbed and reduced species.
To find the most efficient reduction and desorption conditions.

2.0 INTRODUCTION
Temperature Programmed Reduction (TPR)
The TPR analysis allows determining the number and quantity of the reducible species present in
the sample and the temperature at which the reduction itself takes place as a function of the flow
conditions, the percentage of reactive gas, the quantity of sample and the speed of the temperature
increase.
The gas used for this type of analysis is a mixture of reactive gas with an inert gas, as hydrogen in
argon or nitrogen at 5 or 10%. Generally the sample is previously oxidized or pretreated to
eliminate possible contaminants and completely oxidize the metal portion of the catalyst.
Also for this type of analysis the sample is submitted to a linear increase of temperature and to a
constant flow of the gas mixture. The reaction generally starts at room temperature, but at an
extremely low speed, therefore negligible. At a certain temperature, the reaction speed becomes
considerable and the hydrogen consumption can be monitored through the TCD detector. The
signal integration allows calculating the quantity of hydrogen consumed and therefore the number
of reacting sites. The TPR analysis also allows checking the presence of different states of
oxidation of the contained metals.
The presence of different states of oxidation of the contained metals in the sample can also be
investigated with this technique. The peak maximum temperature (T
m
) is the characteristic of the
reduction process and this is used for sample identification and to calculate the reduction activation
energy.

Temperature Programmed Desorption (TPD)

Generally, TPD of O
2
analysis allows the determination of strength, the amount and the type of
active sites available on the surface of a sample by determination of the quantity of gas desorbed
from the sample, which is subjected to a linear temperature ramp.
The sample is initially degassed or pretreated to remove contaminants, such as moisture that is
naturally adsorbed on the sample surface. Then, a constant flow of reactive gas is conveyed onto
the sample to allow the reaction between the sample active sites and the reactive gas according to a
known stoichiometry. After the chemisorption of the reactive gas is completed, desorption process

119
is performed by linearly increasing the temperature of the system. An inert gas (nitrogen, helium or
argon) is flowed through the sample, which acts as carrier gas for the molecules of reactive gas
desorbing from the sample. When the temperature exceeds the E
act
of the gas-solid system is
reached, the bond between the atoms of adsorbate and adsorbent is broken, and the phenomenon of
programmed thermal desorption takes place. The difference of concentration of the desorbed gas
versus a reference flow was measured by using a TCD.

3.0 EQUIPMENT TPDRO

Simplified Schematic Drawing of Temperature Programmed Technique

6. Read and understand the theory of Temperature Programmes Techniques.
7. Read and understand the equipment used in the experiment (TPDRO).
Appendix A.
Pure metal oxide
1. Copper Oxide, CuO
2. Zink Oxide, ZnO
3. Vanadyl Pyrophosphate, (VO)
2
P
2
O
7


120

5.1 Chemical Hazards (refer MSDS for more details)
Copper Oxide (CuO) solid is harmful if swallowed. It is harmful to aquatic organism and may
cause long term adverse effect to the aquatic environment.
Zinc Oxide (ZnO) solid is hazardous in case of inhalation. Slightly hazardous in case of skin
contact (irritant), eye contact (irritant) or ingestion.
Vanadyl Pyrophosphate (VO)
2
P
2
O
7
solid will cause irritation to eyes, sensitization by skin
contact and may cause long term adverse effect to the aquatic environment.



121
6.0 EXPERIMENTS
Temperature Programmed Reduction (TPR)

1. TPR in H
2
analyses were done by using a TPDRO equipment utilising a TCD. The TPR in
H
2
analyses began with the pretreatment process on the metal oxide sample, which involved
two stages.
2. In the first stage, a metal oxide sample (~0.0200 g) was cleaned by using a purified nitrogen
flow (1 bar, 20 cm
3
min
-1
) held constantly for 5 min.
3. In the second stage, the metal oxide sample was cleaned by heating (20 K min
-1
) from room
temperature to 473 K in a purified nitrogen flow (1 bar, 20 cm
3
min
-1
) and held to that flow
at 473 K for 10 min before cooling to room temperature.
4. The pretreatment process was necessary to remove moisture content in the metal oxide
sample and the contaminants from the atmosphere.
5. Then, the flow was switched to 5% hydrogen in nitrogen (1 bar, 25 cm
3
min
-1
) stream and
the temperature was raised to 1173 K at a ramp of 20 K min
-1
.
6. The TPR in H
2
profile, which is a plot of the hydrogen consumption of a metal oxide
sample as a function of temperature, was obtained by using TPDRO software.

Temperature Programmed Desorption (TPD)

1. TPD of O
2
analyses were done by using a TPDRO equipment utilising a TCD. The TPD of
O
2
analyses began with the pretreatment process on the metal oxide sample, which involved
three stages.
2. In the first stage, a metal oxide sample (~0.0200 g) was cleaned by using a purified nitrogen
flow (1 bar, 25 cm
3
min
-1
) held constantly for 10 min.
3. In the second stage, the metal oxide sample was subjected to a purified oxygen flow (1 bar,
25 cm
3
min
-1
) with heating (10 K min
-1
) from room temperature to 673 K and held to that
flow at 673 K for 30 min before cooling to room temperature.
4. During this stage, a reaction between the oxygen and the active sites was conducted. Then,
the metal oxide sample was cleaned again in a purified nitrogen flow (1 bar, 25 cm
3
min
-1
)
for 10 min.
5. The pretreatment process was necessary to remove moisture content in the metal oxide
sample and the contaminants from the atmosphere.
6. Subsequently, the flow was switched to purified helium (1 bar, 25 cm
3
min
-1
) stream and the
temperature was raised to 1173 K at a ramp of 10 K min
-1
.
7. The purified helium gas acted as a carrier gas for the desorbed oxygen from the sample.
8. The TPD of O
2
profile, which is a plot of the amount of oxygen desorbed from the metal
oxide sample as a function of temperature, was obtained by using TPDRO software.


122
1. Identify the optimum reduction and desorption temperatures in the pretreatment of
pure metal oxide by analysing both TPR and TPD profiles.

2. Calculate the total amount of the reducible species (data) from the metal oxide
samples.

3. Calculate the activation reduction and desorption energies for the optimum reduction
and desorption peaks.


123
Appendix A
Material Safety Data Sheet (MSDS)

Ethyl Acetate

Common Synonyms Ethyl ethanoate, acetic acid ethyl ester, ethanoic acid ethyl ester
Formula CH
3
COOC
2
H
5

Physical Properties Form : colourless liquid with a sweet, fruity smell
Stability : stable, but highly flammable
Melting point : -84C
Boiling point : 77C
Water solubility : soluble
Specific gravity : 0.9
Flash point : -4C
Principal Hazards Ethyl acetate is very flammable.
Safe Handling Wear safety glasses. Make sure that there is no source of ignition near
where you work. The vapour may be ignited by contact with a hot plate or
hot water pipe - no naked flame is needed.
Emergency Eye contact : Immediately flush the eye with plenty of water. If
irritation persists call for medical help.
Skin contact : Wash off with water.
If swallowed : Flush the mouth out with water if the person is
conscious. If the amount swallowed is substantial call for
medical help.
Disposal Small amounts of ethyl acetate can be flushed down a sink with a large
quantity of water, unless local rules prohibit this. This material is very
flammable, so care must be taken to avoid any build-up of vapour in sink or
sewers.
Protective Equipment Safety glasses. If gloves are required, use polyvinyl alcohol (PVA).
Source: http://cartwright.chem.ox.ac.uk/hsci/chemicals/ethyl_acetate.html, January 16, 2004


124

8odium Hydroxide

Common Synonyms Caustic soda, soda lye
Formula NaOH
Physical Properties Form : White semi-transparent solid, often supplied as pellets
weighing about 0.1g.
Stability : Stable, but hygroscopic. Absorbs CO
2
from the air.
Melting point : 318C
Water solubility : high (dissolution is very exothermic)
Principal Hazards Contact with the eyes can cause serious long-term damage.
The solid and its solutions are corrosive.
Significant heat is released when sodium hydroxide dissolves in water.
Safe Handling Always wear safety glasses. Do not allow solid or solution to come into
contact with your skin. When preparing solutions swirl the liquid
constantly to prevent "hot spots" developing.
Emergency Eye contact : Immediately flush the eye with plenty of water. Continue
for at least ten minutes and call for immediate medical
help.
Skin contact : Wash off with plenty of water. Remove any
contaminated clothing. If the skin reddens or appears
damaged, call for medical aid.
If swallowed : If the patient is conscious, wash out the mouth well with
water. Do not try to induce vomiting. Call for immediate
medical help.
Disposal Small amounts of dilute sodium hydroxide can be flushed down a sink with
a large quantity of water, unless local rules prohibit this. Larger amounts
should be neutralised before disposal.
Protective Equipment Always wear safety glasses when handling sodium hydroxide or its
solutions. If you need gloves, neoprene, nitrile or natural rubber are
suitable for handling solutions at concentrations of up to 70%
Source: http://cartwright.chem.ox.ac.uk/hsci/chemicals/sodium_hydroxide.html, August 31, 2006

125

Ethyl Alcohol {Ethanol}

Common Synonyms Ethanol, alcohol, grain alcohol, fermentation alcohol, fermentation ethanol
Formula C
2
H
5
OH
Physical Properties Form : colourless fragrant liquid
Stability : stable, but highly flammable
Melting point : -144C
Boiling point : 78C
Water solubility : miscible in all proportions
Explosion limits : 3.3 - 24.5%
Principal Hazards Contact with the eyes can cause considerable irritation.
"One-off" consumption of small amounts of ethanol is not likely to be
harmful, but consumption of large amounts can be (and has been) fatal.
Chronic (long-term) ingestion of ethanol may lead to damage to a
variety of organs, such as the liver, and may increase the risk of cancer.
Ethanol is very flammable, so constitutes a fire risk.
Safe Handling Wear safety glasses. Ensure that no sources of ignition, such as a gas flame,
hot plate or hot air gun, are present in the working area. Check that
ventilation is good; use a fume cupboard if possible.
Emergency Eye contact : Flush the eye with plenty of water. If irritation persists
call for medical help.
If swallowed : If the quantity swallowed is large, call for medical help
Disposal Small amounts of ethanol can be flushed down a sink with a large quantity
of water, unless local rules prohibit this. Do not forget that this material is
very flammable, so precautions must be taken to ensure that flammable
vapour does not build up in the sink or drains.
Protective Equipment Safety glasses
Source: http://cartwright.chem.ox.ac.uk/hsci/chemicals/ethyl_alcohol.html, August 9, 2004

126

8odium Acetate

Common Synonyms Sodium ethanoate, ethanoic acid sodium salt
Formula CH3COONa
Physical Properties Form : white crystalline powder
Stability : Stable
Melting point : 58C
Boiling point : decomposes at temperatures above about 120 C
Water solubility : high
Principal Hazards Sodium acetate may be harmful if a large amount is swallowed.
Safe Handling Wear safety glasses if required by local rules.
Emergency Eye contact : Immediately flush the eye with water. If irritation
persists, call for medical help.
If swallowed : Call for medical help if the amount swallowed is large.
Disposal Small amounts can be washed down the sink unless local rules prohibit this.
Protective Equipment Safety glasses if required by local rules.
Source: http://cartwright.chem.ox.ac.uk/hsci/chemicals/sodium_acetate.html, April 2, 2005

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